CN103013398A - Peelable pressure-sensitive adhesive composition, peelable pressure-sensitive adhesive layer, and peelable pressure-sensitive adhesive sheet - Google Patents

Peelable pressure-sensitive adhesive composition, peelable pressure-sensitive adhesive layer, and peelable pressure-sensitive adhesive sheet Download PDF

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Publication number
CN103013398A
CN103013398A CN2012103533193A CN201210353319A CN103013398A CN 103013398 A CN103013398 A CN 103013398A CN 2012103533193 A CN2012103533193 A CN 2012103533193A CN 201210353319 A CN201210353319 A CN 201210353319A CN 103013398 A CN103013398 A CN 103013398A
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methyl
mass parts
peeling
acrylic acid
acid polymer
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山形真人
冈本昌之
重富清惠
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Nitto Denko Corp
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Nitto Denko Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
    • Y10T428/2891—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a peelable pressure-sensitive adhesive composition, a peelable pressure-sensitive adhesive layer, and a peelable pressure-sensitive adhesive sheet. A peelable pressure-sensitive adhesive composition includes: 100 parts by mass of a polymer (A) having a glass transition temperature lower than 0 DEG C; and 0.05 parts by mass to 3 parts by mass of a (meth)acrylic polymer (B) that has a weight average molecular weight of 1000 or more and less than 30000 and that contains, as a monomer unit, a (meth)acrylic monomer having an alicyclic structure represented by the following general formula (1): CH2-C(R1)COOR2 (1) [wherein, R1 is a hydrogen atom or methyl group and R2 is an alicyclic hydrocarbon group having an alicyclic structure].

Description

Peel off again with binder composition, peel off again with binder layer and adhesive sheet
Technical field
The present invention relates to peel off again with binder composition, have peeling off again with binder layer and peeling off again and use adhesive sheet of said composition.Of the present invention peeling off again for example can be as the surface that is bonded on the adherend time protection adherend, and the surface protective plate that can easily peel off again after use with adhesive sheet.Wherein, especially can be used as the optics surface protective plate for the protection of the surface of the optics such as Polarizer, wave plate, optical compensating film, reflector plate, can also be as be pasted with the belt surface screening glass optical thin film that optics is used surface protective plate at this optics.
Background technology
Known have be bonded on the adherend and the adhesive sheet of peeling off again usefulness through being stripped from behind the certain hour.For example, surface protective plate is attached on the protective by the tackiness agent that is coated on the surface protective plate side usually, is used for the damage, the dirt that prevent that protected body from producing when processing, conveyance.And surface protective plate is stripped from removal (peeling off again) when becoming unwanted.As protected body; known have Stainless Steel Products, plastics, a sheet glass etc.; but the damage of the optics (optical thin film) that attaches for the liquid crystal cells that prevents at liquid-crystal display in recent years,, dirt etc. and be pasted with surface protective plate (optics surface protective plate).
As previously mentioned, surface protective plate is stripped from removal when becoming unwanted, yet from the viewpoint of operation efficiency, in the majority by situation about peeling off with higher speed.Therefore, if the bounding force when peeling off at a high speed is large, then there is the problem that operation efficiency is poor, can damage the protected bodies such as optics, glass when peeling off.On the other hand, if the bounding force when thinking fully to reduce to peel off at a high speed, the bounding force when then low speed is peeled off sometimes also reduces, and occurs floating, peeling off such problem after the punch process of protected body, the milled processed of end face.In addition, when surface protective plate is used as the purposes on the surface of protecting optics, sometimes directly implement the inspection operation of adherend with the state that is pasted with surface protective plate, require surface protective plate self to have high transparent.
For such requirement; good as the high speed separability; quick travel (zipping) can not occur; can not pollute adherend and peeling force after peeling off with the little surface protective plate of the variation of peeling rate; a kind of surface protective plate has been proposed; it is coated in screening glass and forms on the supporter with pressure adhesive, described screening glass pressure adhesive is that to be used in combination second-order transition temperature in (methyl) below certain value acrylic acid polymer be (methyl) acrylic acid polymer more than the certain value at second-order transition temperature; and crosslinking reaction is proceeded to gel fraction reach more than the certain value and obtain (with reference to patent documentation 1).Yet the cementability when its low speed is peeled off sometimes is poor, and especially the transparency can't be met.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2005-146151 communique
Summary of the invention
Therefore, expect that a kind of peeling off again use adhesive sheet, the bonding force when the little and low speed of the bounding force when it is peeled off is at a high speed peeled off is high to not producing the degree of floating, peeling off such problem, particularly transparent high.
An embodiment of the invention are to peel off to use binder composition again.This is peeled off with binder composition and is characterised in that, it comprises: second-order transition temperature is lower than 0 ℃ polymkeric substance (A) 100 mass parts; And weight-average molecular weight is more than 1000 and is lower than (methyl) acrylic acid polymer (B) 0.05 mass parts of 30000 ~ 3 mass parts, and described (methyl) acrylic acid polymer (B) comprises represented (methyl) acrylic monomer with ester ring type structure of following general formula (1) as monomeric unit.
CH 2=C（R 1）COOR 2（1）
[in the formula (1), R 1Be hydrogen atom or methyl, R 2For having the ester ring type alkyl of ester ring type structure]
The screening glass that patent documentation 1 is put down in writing is with disclosing following content in the pressure sensitive adhesives: be (methyl) acrylic acid polymer 100 mass parts below-40 ℃ with respect to second-order transition temperature; the compounding second-order transition temperature is (methyl) acrylic acid polymer 5 ~ 20 mass parts more than 80 ℃, and the such carbonatoms of wherein said (methyl) acrylic acid polymer preferable methyl methyl acrylate is 1 ~ 4 alkyl methacrylate.But during high (methyl) acrylic acid polymer of low with respect to the second-order transition temperature so above second-order transition temperature of (methyl) acrylic acid polymer compounding 5 mass parts, the transparency can significantly reduce.Therefore, of the present invention peeling off with binder composition again is characterised in that, be lower than 0 ℃ polymkeric substance (A) 100 mass parts with respect to second-order transition temperature, the compounding weight-average molecular weight is more than 1000 and is lower than 30000, especially comprise (methyl) acrylic monomer with ester ring type structure as (methyl) acrylic acid polymer (B) 0.05 mass parts of monomeric unit ~ 3 mass parts, it plays following effect: guarantee the transparency, and the bounding force when peeling off at a high speed is low, and the bonding force of low speed when peeling off is also fully high to not floating, peel off the degree of such problem.
Peeling off again with in the binder composition of above-mentioned embodiment, aforementioned polymer (A) also can be acrylic acid polymer.
Peeling off again with in the binder composition of above-mentioned embodiment, the ester ring type alkyl with ester ring type structure of (methyl) acrylic acid polymer (B) can have caged scaffold.In addition, the second-order transition temperature of (methyl) acrylic acid polymer (B) can be 20 ℃ ~ 300 ℃.
Another embodiment of the present invention is used binder layer for peeling off again.This is peeled off with binder layer again and is formed by peeling off with binder composition again of above-mentioned any embodiment.Peeling off again with in the binder layer of this embodiment, can also comprise the insoluble composition of solvent of 85.00 quality % ~ 99.95 quality %.
An again embodiment of the present invention is used adhesive sheet for peeling off again.This is peeled off and comprises peeling off again of above-mentioned any embodiment with adhesive sheet and use binder layer.
Peeling off again with in the adhesive sheet of above-mentioned embodiment, supporter also can be the plastic basis material that forms through antistatic treatment.
An again embodiment of the present invention is surface protective plate.This surface protective plate comprises peeling off again of above-mentioned any embodiment and uses adhesive sheet.
And then, the present invention includes this surface protective plate is used for the optics of surface protection of optical thin film with surface protective plate and the belt surface screening glass optical thin film that is pasted with this optics usefulness surface protective plate.
Description of drawings
Fig. 1 is the schematic side view of the low speed stripping test (permanent load is peeled off) of explanation embodiments of the invention.
Fig. 2 is the schematic side view of the high speed stripping test (180 ° of peel adhesion) of explanation embodiments of the invention.
Embodiment
Below, enumerate that the present invention preferred embodiment being described, but the present invention is not limited by it, only is illustration of the present invention.
Peeling off with binder composition again of present embodiment comprises: as adhesive composition, second-order transition temperature is lower than 0 ℃ polymkeric substance (A) 100 mass parts; And weight-average molecular weight be more than 1000 and be lower than 30000, comprise represented (methyl) acrylic monomer with ester ring type structure of following general formula (1) as (methyl) acrylic acid polymer (B) of monomeric unit (following can suitably be called (methyl) acrylic acid polymer (B)) 0.05 mass parts ~ 3 mass parts.
CH 2=C（R 1）COOR 2（1）
[in the formula (1), R 1Be hydrogen atom or methyl, R 2For having the ester ring type alkyl of ester ring type structure]
Below, polymkeric substance (A), (methyl) acrylic acid polymer (B) peeled off again with the essential composition in the binder composition that belongs to present embodiment is elaborated.
Polymkeric substance (A)
Polymkeric substance (A) if second-order transition temperature be lower than 0 ℃ and then be not particularly limited, can use acrylic acid polymer, rubber series polymkeric substance, silicon-type polymkeric substance, polyurethane series polymkeric substance, polyester based polymer etc. as the normally used various polymkeric substance of tackiness agent.Suitable especially is to be easy to compatible with (methyl) acrylic acid polymer (B) and transparent high acrylic acid polymer.
The second-order transition temperature (Tg) of polymkeric substance (A) is lower than 0 ℃, preferably is lower than-10 ℃, more preferably less than-40 ℃, is generally more than-80 ℃.The second-order transition temperature (Tg) of polymkeric substance (A) is more than 0 ℃ the time, and polymkeric substance is difficult to flow sometimes, and the wetting of adherend become insufficient, and cementability can reduce.
In the present embodiment, when polymkeric substance (A) was multipolymer, its second-order transition temperature was the value of calculating based on formula (2) (Fox formula).
1/Tg=W 1/Tg 1+W 2/Tg 2+…+W n/Tg n（2）
[in the formula (2), Tg be multipolymer second-order transition temperature (unit: K),
Tg i(i=1,2 ... second-order transition temperature when n) expression monomer i forms homopolymer (unit: K),
W i(i=1,2 ... n) mass fraction of expression monomer i in the total monomer composition.]
In addition, the glass transition temperature Tg of monomer i iThe nominal value of putting down in writing for document (such as polymer handbook, bonding handbook etc.), catalogue etc.
Need to prove, in this manual, when homopolymer " form second-order transition temperature " refers to " second-order transition temperature of the homopolymer of this monomer ", only refers to the second-order transition temperature (Tg) of the polymkeric substance that forms as monomer component with a certain monomer (being sometimes referred to as " monomer X ").Particularly, in " Polymer Handbook " (the 3rd edition, John Wiley﹠Sons, Inc, 1989), listed numerical value.In addition, in the aforementioned documents not the second-order transition temperature (Tg) of homopolymer of record refer to the value that for example obtains by following measuring method.Namely, in the reactor that possesses thermometer, agitator, nitrogen ingress pipe and reflux condensing tube, drop into 100 mass parts monomer X, 0.2 mass parts 2,2 '-Diisopropyl azodicarboxylate and 200 mass parts are as the ethyl acetate of polymer solvent, and the limit imports the nitrogen limit and stirred 1 hour.As above operation behind the oxygen in the removal polymerization system, is warming up to 63 ℃ of reactions 10 hours.Then, be cooled to room temperature, obtain the homopolymer solution of solid component concentration 33 quality %.Then, this homopolymer solution casting is coated on the release liner, carries out drying, make the approximately test sample of 2mm (homopolymer of sheet) of thickness.Then, weighing approximately this test sample of 1 ~ 2mg is placed in the aluminum open chamber, use temperature modulation D S C(trade(brand)name " Q-2000 ", TA Instruments Japan Inc. makes), under the nitrogen atmosphere of 50ml/min, with the heat-up rate of 5 ℃/min, the Reversing heat flow (Reversing Heat Flow, specific heat composition) that obtains homopolymer changes.Take JIS-K-7121 as reference, with the second-order transition temperature (Tg) of following temperature when making homopolymer: the temperature of the point of the curved intersection of the equidistant straight line of prolongation straight line of the baseline of the low temperature side of the Reversing heat flow that obtains at longitudinal axis and the baseline of high temperature side and the ladder type changing unit of glass transition.
In addition, the weight-average molecular weight (Mw) of polymkeric substance (A) is 30,000 ~ 5,000,000 for example, is preferably 100,000 ~ 2,000,000, more preferably 200,000 ~ 1,000,000.Weight-average molecular weight (Mw) is lower than at 30,000 o'clock, sometimes the force of cohesion of tackiness agent not enough, be easy to produce the pollution to adherend.On the other hand, weight-average molecular weight (Mw) surpasses at 5,000,000 o'clock, sometimes the mobile step-down of tackiness agent, the wetting deficiency to adherend, cementability reduction.
Below the acrylic acid polymer as the suitable concrete example of polymkeric substance (A) is elaborated.
Acrylic acid polymer for example for contain more than the 50 quality % with (methyl) alkyl acrylate of the alkyl of the straight or branched of carbonatoms 1 ~ 20 polymkeric substance as monomeric unit.In addition, acrylic acid polymer can be made the independent or two or more formations that combine of (methyl) alkyl acrylate of the alkyl with carbonatoms 1 ~ 20.The method that obtains acrylic acid polymer is not particularly limited, can the applying soln polymerization, letex polymerization, mass polymerization, suspension polymerization, radiation-curing polymerization etc. be as the synthetic method of acrylic acid polymer and normally used various polymerization process obtains this polymkeric substance.With peeling off again with adhesive sheet when the surface protective plate described later of present embodiment, can use aptly solution polymerization, letex polymerization.
Ratio about (methyl) alkyl acrylate of alkyl with carbonatoms 1 ~ 20, for example, be 50 quality % ~ 99.9 quality % with respect to the monomer component total amount for the preparation of acrylic acid polymer, be preferably 60 quality % ~ 98 quality %, more preferably 70 quality % ~ 95 quality %.
(methyl) alkyl acrylate as the alkyl with carbonatoms 1 ~ 20 for example can list (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) vinylformic acid isopentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid tetradecyl ester, (methyl) vinylformic acid pentadecyl ester, (methyl) aliphatic acrylate, (methyl) vinylformic acid heptadecyl ester, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid nonadecyl ester, (methyl) vinylformic acid C such as (methyl) vinylformic acid eicosyl ester 1-20Alkyl ester [is preferably (methyl) vinylformic acid C 2-14Alkyl ester, more preferably (methyl) vinylformic acid C 2-10Alkyl ester] etc.Need to prove, (methyl) alkyl acrylate refers to alkyl acrylate and/or alkyl methacrylate, with " (methyl) ... " it is the identical meaning.
In addition, about acrylic acid polymer, with the purpose that is modified as of force of cohesion, thermotolerance, bridging property etc., can also comprise as required can with other monomer component (co-polymerized monomer) of aforementioned (methyl) alkyl acrylate copolymer.Therefore, acrylic acid polymer can also comprise co-polymerized monomer with (methyl) alkyl acrylate as main component.As co-polymerized monomer, can use aptly the monomer with polar group.
As the object lesson of co-polymerized monomer, can list:
Vinylformic acid, methacrylic acid, vinylformic acid carboxyl ethyl ester, vinylformic acid carboxyl pentyl ester, methylene-succinic acid, toxilic acid, fumaric acid, β-crotonic acid, iso-crotonic acid etc. contain carboxylic monomer;
The hydroxyl monomers such as (methyl) vinylformic acid hydroxyalkyl acrylate such as (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 8-hydroxyl monooctyl ester, (methyl) vinylformic acid 10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) vinylformic acid 12-hydroxyl lauryl, methacrylic acid (4-hydroxymethyl cyclohexyl) methyl esters;
Maleic anhydride, itaconic anhydride etc. contain the anhydride group monomer;
Styrene sulfonic acid, allyl sulphonic acid, 2-(methyl) acrylamide-2-methylpro panesulfonic acid, (methyl) acrylamide propanesulfonic acid, (methyl) vinylformic acid sulfonic acid propyl ester, (methyl) acryloxy naphthene sulfonic acid etc. contain the sulfonic group monomer;
The phosphorous acidic group monomers such as 2-hydroxyethyl acryloyl phosphoric acid ester;
(methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N, N-dipropyl (methyl) acrylamide, N, N-di-isopropyl (methyl) acrylamide, N, N-two (normal-butyl) (methyl) acrylamide, N, the N such as N-two (tertiary butyl) (methyl) acrylamide, N-dialkyl group (methyl) acrylamide; N-ethyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, N-butyl (methyl) acrylamide, N-normal-butyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide, N-hydroxymethyl-propane (methyl) acrylamide, N-methoxymethyl (methyl) acrylamide, N-methoxy ethyl (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, (N-replacement) acid amides such as N-acryloyl morpholine are monomer;
The N-(methyl) acryloyl-oxy methylene succinimide, N-(methyl) acryl-6-oxa-hexa-methylene succinimide, N-(methyl) acryl-succinimides such as 8-oxa-eight methylene radical succinimides are monomer;
The maleimides such as N-N-cyclohexylmaleimide, N-sec.-propyl maleimide, N-lauryl maleimide, N-phenylmaleimide are monomer;
The clothing health imide series monomers such as N-methyl clothing health imide, N-ethyl clothing health imide, N-butyl clothing health imide, N-octyl group clothing health imide, N-2-ethylhexyl clothing health imide, N-cyclohexyl clothing health imide, N-lauryl clothing health imide;
The vinyl ester such as vinyl-acetic ester, propionate;
NVP, N-methyl ethylene pyrrolidone, the N-vinyl pyridine, N-vinyl piperidone, the N-vinyl pyrimidine, N-vinyl piperazine, the N-vinylpyrazine, the N-vinyl pyrrole, the N-vinyl imidazole, N-Yi Xi Ji oxazole, the N-(methyl) acryl-2-Pyrrolidone, the N-(methyl) acryl piperidines, the N-(methyl) acryl tetramethyleneimine, N-vinyl morpholine, N-vinyl-2-piperidone, N-vinyl-3-morpholone mai, N-vinyl-2-hexanolactam, N-vinyl-1,3-oxazine-2-ketone, N-vinyl-3, the 5-morpholine diketone, N-vinyl pyrazoles, N-Yi thiazolinyl isoxazole, the N-vinylthiazole, N-vinyl isothiazole, the nitrogen-containing hetero ring system monomers such as N-vinyl pyridazine;
N-vinyl carboxylic acid amides;
The lactan such as N-caprolactam are monomer;
The cyanoacrylate monomer such as vinyl cyanide, methacrylonitrile;
(methyl) acrylic-amino ethyl ester, (methyl) vinylformic acid N, N-dimethylamino ethyl ester, (methyl) vinylformic acid N, (methyl) acrylic-amino alkyl esters such as N-dimethylamino ethyl ester, (methyl) vinylformic acid tertiary butyl amino ethyl ester are monomer;
(methyl) alkoxyalkyl acrylates such as (methyl) vinylformic acid methoxyl group ethyl ester, (methyl) vinylformic acid ethoxy ethyl ester, (methyl) vinylformic acid propoxy-ethyl ester, (methyl) vinylformic acid butoxyethyl, (methyl) vinylformic acid oxyethyl group propyl ester are monomer;
The styrenic monomers such as vinylbenzene, alpha-methyl styrene;
(methyl) glycidyl acrylate etc. contains the epoxy group(ing) acrylic monomer; The alcohol such as (methyl) polyalkylene glycol acrylate ester, (methyl) vinylformic acid polypropylene glycol ester, (methyl) vinylformic acid methoxyl group glycol ester, (methyl) vinylformic acid methoxyl group polypropylene glycol ester are acrylate monomer;
(methyl) tetrahydrofurfuryl acrylate, contain fluorine atoms (methyl) acrylate, organosilicon (methyl) acrylate etc. have the acrylic ester monomer of heterocycle, halogen atom, Siliciumatom etc.;
The ethylene series monomers such as isoprene, divinyl, iso-butylene;
The vinyl ether such as methylvinylether, ethyl vinyl ether is monomer;
The vinyl ester such as vinyl-acetic ester, propionate;
The aromatic ethenyl compound such as Vinyl toluene, vinylbenzene;
Alkene or the dienes such as ethene, divinyl, isoprene, iso-butylene;
The vinyl ethers such as vinyl alkyl ethers;
Vinylchlorid;
Sodium vinyl sulfonates etc. contain the sulfonic group monomer;
N-cyclohexylmaleimide, sec.-propyl maleimide etc. contain the imide monomer;
(methyl) vinylformic acid 2-isocyanato ethyl etc. contains the isocyanate group monomer;
Acryloyl morpholine;
(methyl) vinylformic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, dicyclo amyl group (methyl) acrylate (methacrylic acid three rings [5.2.1.02,6] last of the ten Heavenly stems-8-base ester, Dicyclopentanyl Methacrylate) etc. have (methyl) acrylate of ester ring type alkyl;
(methyl) phenyl acrylate, (methyl) vinylformic acid phenoxy ethyl etc. have (methyl) acrylate of aromatic hydrocarbyl;
(methyl) acrylate that is obtained by terpene compound derivative alcohol; Deng.
Need to prove, these co-polymerized monomers can use separately or be used in combination of two or more.
Acrylic acid polymer is with, using aptly the hydroxyl monomer, contain carboxylic monomer when alkyl acrylate contains co-polymerized monomer as (methyl) of main component.Wherein, as the hydroxyl monomer, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 4-hydroxyl butyl ester can be used aptly, as containing carboxylic monomer, vinylformic acid can be used aptly.Consumption as co-polymerized monomer, be not particularly limited, usually with respect to the monomer component total amount for the preparation of aforementioned acrylic acid polymer, can contain 0.01 quality % ~ 40 quality %, preferably contain 0.1 quality % ~ 30 quality %, more preferably contain 0.5 quality % ~ 20 quality % co-polymerized monomers.
By containing the co-polymerized monomer more than the 0.01 quality %, the force of cohesion that can prevent from having the acrylic pressure-sensitive adhesive sheet of the binder layer that is formed by acrylic adhesive composition reduces, and prevents the pollution when peeling off from adherend.In addition, be below the 40 quality % by the content that makes co-polymerized monomer, can prevent that force of cohesion from becoming too high, improve the adhesion sense of normal temperature (25 ℃).
In addition, in order to adjust the force of cohesion of formed acrylic adhesive composition, acrylic acid polymer can also contain multi-functional monomer as required.
As multi-functional monomer, for example can list two (methyl) vinylformic acid (gathering) glycol ester, two (methyl) vinylformic acid (gathering) propylene glycol ester, two (methyl) vinylformic acid DOPCP, two (methyl) vinylformic acid pentaerythritol ester, three (methyl) vinylformic acid pentaerythritol ester, six (methyl) vinylformic acid dipentaerythritol ester, two (methyl) vinylformic acid 1, the 2-glycol ester, two (methyl) vinylformic acid 1,6-hexylene glycol ester, two (methyl) vinylformic acid 1,12-dodecanediol ester, three (methyl) vinylformic acid trishydroxymethyl propyl ester, three (methyl) vinylformic acid tetra methylol methyl esters, (methyl) allyl acrylate, (methyl) vinyl acrylate, Vinylstyrene, epoxy acrylate, polyester acrylate, urethane acrylate, two (methyl) butyl acrylate, two (methyl) Ethyl acrylate etc.Wherein, can use aptly three (methyl) vinylformic acid trishydroxymethyl propyl ester, two (methyl) vinylformic acid hexylene glycol ester, six (methyl) vinylformic acid dipentaerythritol ester.Multifunctional (methyl) acrylate can use separately or be used in combination of two or more.
Consumption as multi-functional monomer, can be different because of its molecular weight, functional group's number etc., but with respect to the monomer component total amount for the preparation of acrylic acid polymer, can be added into 0.01 quality % ~ 3.0 quality %, be preferably 0.02 quality % ~ 2.0 quality %, 0.03 quality % ~ 1.0 quality % more preferably.
With respect to the monomer component total amount for the preparation of acrylic acid polymer, when the consumption of multi-functional monomer surpasses 3.0 quality %, for example, the force of cohesion of acrylic adhesive composition can become too high sometimes, bonding force (high speed peeling force, low speed peeling force) can reduction.On the other hand, when being lower than 0.01 quality %, for example, the force of cohesion of acrylic adhesive composition can reduce, can pollute when peeling off from adherend (protected body) sometimes.
When the preparation acrylic acid polymer, utilize based on the heat, the ultraviolet curing reaction that have used the polymerization starters such as thermal polymerization, Photoepolymerizationinitiater initiater (light trigger), can easily form acrylic acid polymer.Especially from shortening the advantage grade of polymerization time, can use aptly thermal polymerization.Polymerization starter can use separately or be used in combination of two or more.
As thermal polymerization, (for example for example can list azo and be polymerization starter, 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo is two-the 2-methylbutyronitrile, 2,2 '-two (2 Methylpropionic acid) dimethyl esters of azo, 4,4 '-azo is two-the 4-cyanopentanoic acid, the two isovaleronitriles of azo, 2,2 '-two (2-amidine propane) dihydrochlorides of azo, 2,2 '-azo two [2-(5-methyl-2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride, 2,2 '-two (the 2-methyl-prop amidine) dithionates of azo, 2,2 '-two (N, the N '-dimethylene isobutyl-amidino groups) dihydrochlorides of azo etc.); Peroxidation system polymerization starter (for example, dibenzoyl peroxide, tert-butyl hydroperoxide maleic acid ester (t-butyl peroxide maleate), lauroyl peroxide etc.); Reducto oxydative system polymerization starter etc.
Consumption as thermal polymerization is not particularly limited, and for example, with respect to monomer component 100 mass parts of preparation acrylic acid polymer, carries out compounding with 0.01 mass parts ~ 5 mass parts, the amount that is preferably in the scope of 0.05 mass parts ~ 3 mass parts.
As Photoepolymerizationinitiater initiater; be not particularly limited; for example, can use benzoin ether is that Photoepolymerizationinitiater initiater, methyl phenyl ketone are that Photoepolymerizationinitiater initiater, α-keto-alcohol are that Photoepolymerizationinitiater initiater, aromatic sulfonyl are that Photoepolymerizationinitiater initiater, photolytic activity oxime are that Photoepolymerizationinitiater initiater, bitter almond oil camphor are that Photoepolymerizationinitiater initiater, benzil are that Photoepolymerizationinitiater initiater, benzophenone series Photoepolymerizationinitiater initiater, ketal are that Photoepolymerizationinitiater initiater, thioxanthone are that Photoepolymerizationinitiater initiater, acylphosphine oxide are Photoepolymerizationinitiater initiater etc.
Particularly, be Photoepolymerizationinitiater initiater as benzoin ether, for example can list benzoin methyl ether, bitter almond oil camphor ethyl ether, bitter almond oil camphor propyl ether, bitter almond oil camphor isopropyl ether, bitter almond oil camphor isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-ketone [trade(brand)name: Irgacure 651, BASF AG make], methyl-phenoxide methyl ether (anisole methyl ether) etc.Be Photoepolymerizationinitiater initiater as methyl phenyl ketone, such as listing 1-hydroxycyclohexylphenylketone [trade(brand)name: Irgacure 184, BASF AG make], 4-phenoxy group dichloroacetophenone, the 4-tertiary butyl-dichloroacetophenone, 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone [trade(brand)name: Irgacure 2959, BASF AG make], 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone [trade(brand)name: DAROCUR 1173, BASF AG make], methoxyacetophenone etc.Be Photoepolymerizationinitiater initiater as α-keto-alcohol, such as listing 2-methyl-2-hydroxypropiophenonepreparation, 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2-methyl propane-1-ketone etc.Be Photoepolymerizationinitiater initiater as aromatic sulfonyl, such as listing 2-naphthalic sulfonic chloride etc.Be Photoepolymerizationinitiater initiater as the photolytic activity oxime, for example can list 1-phenyl-1,1-propane diketone-2-(O-ethoxy carbonyl)-oxime etc.
In addition, bitter almond oil camphor is to comprise in the Photoepolymerizationinitiater initiater such as bitter almond oil camphor etc.Benzil is to comprise in the Photoepolymerizationinitiater initiater such as benzil etc.For example comprise in the benzophenone series Photoepolymerizationinitiater initiater benzophenone, benzoylbenzoic acid, 3,3 '-dimethyl-4-methoxy benzophenone, polyvinyl benzophenone, Alpha-hydroxy cyclohexyl-phenyl ketone etc.Ketal is to comprise in the Photoepolymerizationinitiater initiater such as benzil dimethyl ketal etc.Thioxanthone is to comprise for example thioxanthone, CTX, 2-methyl thioxanthone, 2 in the Photoepolymerizationinitiater initiater, 4-dimethyl thioxanthone, isopropyl thioxanthone, 2,4-two clopenthixal ketones, 2,4-diethyl thioxanthone, isopropyl thioxanthone, 2,4-di-isopropyl thioxanthone, dodecyl thioxanthone etc.
Be Photoepolymerizationinitiater initiater as acylphosphine oxide; for example can list two (2; 6-dimethoxy benzoyl) phenyl phosphine oxide; two (2; 6-dimethoxy benzoyl) (2; 4; the 4-tri-methyl-amyl) phosphine oxide; two (2; 6-dimethoxy benzoyl)-the normal-butyl phosphine oxide; two (2; 6-dimethoxy benzoyl)-(2-methylpropane-1-yl) phosphine oxide; two (2; 6-dimethoxy benzoyl)-(1-methylpropane-1-yl) phosphine oxide; two (2; 6-dimethoxy benzoyl)-tertiary butyl phosphine oxide; two (2; 6-dimethoxy benzoyl) cyclohexyl phosphine oxide; two (2; 6-dimethoxy benzoyl) octyl group phosphine oxide; two (2-methoxybenzoyls) (2-methylpropane-1-yl) phosphine oxide; two (2-methoxybenzoyls) (1-methylpropane-1-yl) phosphine oxide; two (2; 6-diethoxy benzoyl) (2-methylpropane-1-yl) phosphine oxide; two (2; 6-diethoxy benzoyl) (1-methylpropane-1-yl) phosphine oxide; two (2; 6-dibutoxy benzoyl) (2-methylpropane-1-yl) phosphine oxide; two (2; 4-dimethoxy benzoyl) (2-methylpropane-1-yl) phosphine oxide; two (2; 4; 6-Three methyl Benzene formyl) (2; 4-two pentyloxy phenyl) phosphine oxide; two (2; 6-dimethoxy benzoyl) benzyl phosphine oxide; two (2; 6-dimethoxy benzoyl)-2-phenyl propyl phosphine oxide; two (2; 6-dimethoxy benzoyl)-2-phenylethyl phosphine oxide; two (2; 6-dimethoxy benzoyl) benzyl phosphine oxide; two (2; 6-dimethoxy benzoyl)-2-phenyl propyl phosphine oxide; two (2; 6-dimethoxy benzoyl)-2-phenylethyl phosphine oxide; 2; 6-dimethoxy benzoyl benzyl butyl phosphine oxide; 2; 6-dimethoxy benzoyl benzyl octyl group phosphine oxide; two (2; 4; 6-Three methyl Benzene formyl)-2; 5-diisopropyl phenyl phosphine oxide; two (2; 4; 6-Three methyl Benzene formyl)-2-aminomethyl phenyl phosphine oxide; two (2; 4; 6-Three methyl Benzene formyl)-4-aminomethyl phenyl phosphine oxide; two (2; 4; 6-Three methyl Benzene formyl)-2; 5-diethyl phenyl phosphine oxide; two (2; 4; 6-Three methyl Benzene formyl)-2,3,5; 6-tetramethylphenyl phosphine oxide; two (2; 4,6-Three methyl Benzene formyl)-2,4-two-n-butoxy phenyl phosphine oxide; 2; 4; 6-Three methyl Benzene formyl diphenyl phosphine oxide; two (2,6-dimethoxy benzoyls)-2,4; 4-tri-methyl-amyl phosphine oxide; two (2; 4,6-Three methyl Benzene formyl) isobutyl-phosphine oxide; 2,6-dimethoxy benzoyl-2; 4; 6-Three methyl Benzene formyl-normal-butyl phosphine oxide; two (2,4,6-Three methyl Benzene formyl) phenyl phosphine oxide; two (2; 4; 6-Three methyl Benzene formyl)-2,4-dibutoxy phenyl phosphine oxide; 1,10-two [two (2; 4,6-Three methyl Benzene formyl) phosphine oxide] decane; three (2-toluyl) phosphine oxide etc.
Consumption to Photoepolymerizationinitiater initiater is not particularly limited, and for example, with respect to monomer component 100 mass parts of preparation acrylic acid polymer, carries out compounding with 0.01 mass parts ~ 5 mass parts, the amount that is preferably in the scope of 0.05 mass parts ~ 3 mass parts.
Herein, when the consumption of Photoepolymerizationinitiater initiater was less than 0.01 mass parts, it is insufficient that polyreaction becomes sometimes.When the consumption of Photoepolymerizationinitiater initiater surpasses 5 mass parts, owing to absorbing ultraviolet ray, Photoepolymerizationinitiater initiater cause ultraviolet ray can't arrive binder layer inside sometimes.In this situation, the reduction of percent polymerization occurs sometimes or the molecular weight of the polymkeric substance that generates diminishes.Then, thus, the force of cohesion step-down of the binder layer of formation, when binder layer was peeled off from film, the part of binder layer can remain on the film and film is become and can't recycle sometimes.Need to prove, the optical polymerism initiator can use separately or be used in combination of two or more.
In the present embodiment, acrylic acid polymer also can be prepared with the form of partial polymer (acrylic acid polymer slurries), described partial polymer is the mixture irradiation ultraviolet radiation (UV) that forms with aforementioned monomer composition and polymerization starter compounding, makes that monomer component is partially polymerized to be formed.Can also prepare acrylic adhesive composition by compounding (methyl) described later acrylic acid polymer (B) in the acrylic acid polymer slurries, and this binder composition is coated on the body to be coated of regulation, irradiation ultraviolet radiation stops polymerization.
In addition, the weight-average molecular weight of acrylic acid polymer (Mw) is 30,000 ~ 5,000,000 for example, is preferably 100,000 ~ 2,000,000, more preferably 200,000 ~ 1,000,000.Weight-average molecular weight (Mw) is compared with above-mentioned scope when too small, sometimes the force of cohesion of tackiness agent not enough, be easy to produce the pollution to adherend.On the other hand, weight-average molecular weight (Mw) is compared with above-mentioned scope when excessive, sometimes the mobile step-down of tackiness agent, wetting deficiency, the cementability of adherend reduced.
In addition, the second-order transition temperature of acrylic acid polymer (Tg) is lower than 0 ℃, is preferably to be lower than-10 ℃, more preferably is lower than-40 ℃, is generally more than-80 ℃.The second-order transition temperature (Tg) of acrylic acid polymer (A) is more than 0 ℃ the time, and polymkeric substance is difficult to flow, wetting insufficient, the cementability of adherend reduced sometimes.
In the present embodiment, when acrylic acid polymer was multipolymer, its second-order transition temperature was the value of calculating based on aforementioned formula (2) (Fox formula).
(methyl) acrylic acid polymer (B)
(methyl) acrylic acid polymer (B) is more than 1000 for weight-average molecular weight and is lower than (methyl) acrylic acid polymer of 30000, described (methyl) acrylic acid polymer comprises represented (methyl) acrylic monomer with ester ring type structure of following general formula (1) as monomeric unit, peeling off again with in the acrylic adhesive composition of present embodiment, work as tackifying resin.
CH 2=C（R 1）COOR 2（1）
[in the formula (1), R 1Be hydrogen atom or methyl, R 2For having the ester ring type alkyl of ester ring type structure]
As the ester ring type alkyl R in the general formula (1) 2, can list the ester ring type alkyl such as cyclohexyl, isobornyl, dicyclo amyl group (dicyclopentanyl) etc.As this (methyl) acrylate with ester ring type alkyl, can list such as (methyl) cyclohexyl acrylate with cyclohexyl, (methyl) isobornyl acrylate with isobornyl, (methyl) vinylformic acid such as (methyl) vinylformic acid dicyclo pentyl ester with dicyclo amyl group and the ester of alicyclic alcohol.By make (methyl) acrylic acid polymer (B) with this acrylic monomer with more fluffy structure as monomeric unit, the cementability in the time of can improving low speed and peel off.
And then in the present embodiment, the ester ring type alkyl that consists of (methyl) acrylic acid polymer (B) preferably has caged scaffold.Caged scaffold refers to the above ester ring type structure of three rings.By making (methyl) acrylic acid polymer (B) with this more fluffy structure of caged scaffold, can further improve the cementability of peeling off again with acrylic adhesive composition (peel off again and use acrylic pressure-sensitive adhesive sheet).Especially the cementability in the time of can improving more significantly low speed and peel off.
As the ester ring type alkyl R with caged scaffold 2For example can list represented three cyclopentenyls (tricyclopentenyl) of the represented dicyclo amyl group of following formula (3a), following formula (3b) represented double cyclopentenyl (hexahydro--4,7-methylene radical-1H-indenyl, dicyclopentenyl), following formula (3c) represented adamantyl, following formula (3d) represented three cyclopentyl (tricyclopentanyl), following formula (3e) etc.Need to prove, when synthetic (methyl) acrylic acid polymer (B), adopt in the situation of UV polymerization when making binder composition, from being difficult for producing the viewpoint of polymerization obstacle, among (methyl) acrylic monomer with the ester ring type structure more than three rings with caged scaffold, especially can preferably use the represented dicyclo amyl group of following formula (3a), the represented adamantyl of following formula (3c), three cyclopentyl that following formula (3d) is represented etc. have (methyl) acrylic monomer of saturated structures as the monomer that consists of (methyl) acrylic acid polymer (B).
[Chemical formula 1]
Figure BDA00002167691000181
In addition, example as this (methyl) acrylic monomer with the above ester ring type structure of three rings with caged scaffold can list methacrylic acid dicyclo pentyl ester (dicyclopentanyl methacrylate), vinylformic acid dicyclo pentyl ester (dicyclopentanyl acrylate), methacrylic acid dicyclo amyl group oxygen ethyl ester, vinylformic acid dicyclo amyl group oxygen ethyl ester, methacrylic acid three ring pentyl esters, vinylformic acid three ring pentyl esters, methacrylic acid 1-diamantane ester, vinylformic acid 1-diamantane ester, 2-Methacryloyloxy-2-methyladamantane, vinylformic acid 2-methyl-2-diamantane ester, 2-Ethyl-2-adamantyl methacrylate, vinylformic acid 2-ethyl-(methyl) acrylate such as 2-diamantane ester.Should can use separately or be used in combination of two or more by (methyl) acrylic monomer.
(methyl) acrylic acid polymer (B) of present embodiment can be the homopolymer with (methyl) acrylic monomer of ester ring type structure, perhaps also can be to have (methyl) acrylic monomer of ester ring type structure and the multipolymer of other (methyl) acrylate monomer or co-polymerized monomer.
Example as other (methyl) acrylate monomer can list:
(methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) vinylformic acid isopentyl ester, (methyl) Ethyl acrylate, (methyl) ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) alkyl acrylate that (methyl) dodecylacrylate is such;
(methyl) phenyl acrylate, such (methyl) vinylformic acid aryl ester of (methyl) benzyl acrylate;
(methyl) acrylate that is obtained by terpene compound derivative alcohol; Deng.
This (methyl) acrylate can use separately or be used in combination of two or more.
As the example of co-polymerized monomer, can list:
Vinylformic acid, methacrylic acid, vinylformic acid carboxyl ethyl ester, vinylformic acid carboxyl pentyl ester, methylene-succinic acid, toxilic acid, fumaric acid, β-crotonic acid, iso-crotonic acid etc. contain carboxylic monomer;
(methyl) vinylformic acid methoxyl group ethyl ester, (methyl) vinylformic acid ethoxy ethyl ester, (methyl) vinylformic acid propoxy-ethyl ester, (methyl) vinylformic acid butoxyethyl, such (methyl) alkoxyalkyl acrylate of (methyl) vinylformic acid oxyethyl group propyl ester are monomer;
The salt such as (methyl) alkali metal salts of acrylic acids;
Two (methyl) acrylate monomer of (gathering) aklylene glycol that two (methyl) acrylate of two (methyl) acrylate of two (methyl) acrylate of two (methyl) acrylate of ethylene glycol, two (methyl) acrylate of Diethylene Glycol, triethylene glycol, two (methyl) acrylate of polyoxyethylene glycol, propylene glycol, two (methyl) acrylate of dipropylene glycol, tripropylene glycol is such;
Polynary (methyl) acrylate monomer that trimethylolpropane tris (methyl) acrylate is such;
The vinyl ester such as vinyl-acetic ester, propionate;
Vinylidene chloride, the such vinyl halides based compound of (methyl) vinylformic acid-2-chloroethene ester;
2-vinyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, the 2-pseudoallyl-such De Han of 2-oxazoline oxazolinyl polymerizable compound;
(methyl) acryl aziridine, (methyl) vinylformic acid-2-'-aziridino ethyl ester are such contains the '-aziridino polymerizable compound;
Glycidyl allyl ether, (methyl) vinylformic acid glycidyl ether, (methyl) acrylic acid-2-ethyl glycidyl ether are such contains the epoxy group(ing) vinyl monomer;
The hydroxyl vinyl monomer that the affixture of (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, lactone and (methyl) 2-Hydroxy ethyl acrylate is such;
The end of the polyalkylene glycol that the multipolymer of the multipolymer of polypropylene glycol, polyoxyethylene glycol, polytetramethylene glycol, polytetramethylene glycol, polyoxyethylene glycol and polypropylene glycol, polytetramethylene glycol and polyoxyethylene glycol is such is combined with the macromonomer of the unsaturated groups such as (methyl) acryl, styryl, vinyl;
Fluorine replaces the so fluorine-containing vinyl monomer of (methyl) alkyl acrylate;
Maleic anhydride, itaconic anhydride etc. contain the anhydride group monomer;
The aromatic ethenyl compounds such as vinylbenzene, alpha-methyl styrene, Vinyl toluene are monomer;
2-chloroethyl vinyl ether, monochloro vinyl-acetic ester are such contains the reactive halogen vinyl monomer;
(methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, N-butyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide, N-hydroxymethyl-propane (methyl) acrylamide, N-methoxy ethyl (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, the such amide-containing vinyl monomer of N-acryloyl morpholine;
The N-(methyl) acryloyl-oxy methylene succinimide, N-(methyl) acryl-6-oxa-hexa-methylene succinimide, N-(methyl) acryl-succinimides such as 8-oxa-eight methylene radical succinimides are monomer;
The maleimides such as N-N-cyclohexylmaleimide, N-sec.-propyl maleimide, N-lauryl maleimide, N-phenylmaleimide are monomer;
The clothing health imide series monomers such as N-methyl clothing health imide, N-ethyl clothing health imide, N-butyl clothing health imide, N-octyl group clothing health imide, N-2-ethylhexyl clothing health imide, N-cyclohexyl clothing health imide, N-lauryl clothing health imide;
NVP, N-methyl ethylene pyrrolidone, the N-vinyl pyridine, N-vinyl piperidone, the N-vinyl pyrimidine, N-vinyl piperazine, the N-vinylpyrazine, the N-vinyl pyrrole, the N-vinyl imidazole, N-Yi Xi Ji oxazole, the N-(methyl) acryl-2-Pyrrolidone, the N-(methyl) acryl piperidines, the N-(methyl) acryl tetramethyleneimine, N-vinyl morpholine, N-vinyl pyrazoles, N-Yi thiazolinyl isoxazole, the N-vinylthiazole, N-vinyl isothiazole, the nitrogen-containing hetero ring system monomers such as N-vinyl pyridazine;
N-vinyl carboxylic acid amides;
The lactan such as N-caprolactam are monomer;
The cyanoacrylate monomers such as (methyl) vinyl cyanide;
(methyl) acrylic-amino ethyl ester, (methyl) vinylformic acid N, N-dimethylamino ethyl ester, (methyl) vinylformic acid N, (methyl) acrylic-amino alkyl esters such as N-dimethylamino ethyl ester, (methyl) vinylformic acid tertiary butyl amino ethyl ester are monomer;
N-cyclohexylmaleimide, sec.-propyl maleimide etc. contain the imide monomer;
(methyl) vinylformic acid 2-isocyanato ethyl etc. contains the isocyanate group monomer;
Vinyltrimethoxy silane, γ-methacryloxypropyl trimethoxy silane, allyltrimethoxysilanis, trimethoxy-silylpropyl allyl amine, 2-methoxy ethoxy Trimethoxy silane are such contains organic silico ethylene base monomer;
The hydroxyl monomers such as (methyl) vinylformic acid hydroxyalkyl acrylate such as (methyl) Hydroxyethyl Acrylate, (methyl) vinylformic acid hydroxy propyl ester, (methyl) vinylformic acid hydroxyl butyl ester, the own ester of (methyl) vinylformic acid hydroxyl, (methyl) vinylformic acid hydroxyl monooctyl ester, (methyl) vinylformic acid hydroxyl ester in the last of the ten Heavenly stems, (methyl) vinylformic acid hydroxyl lauryl, methacrylic acid (4-hydroxymethyl cyclohexyl) methyl esters;
(methyl) tetrahydrofurfuryl acrylate, contain fluorine atoms (methyl) acrylate, organosilicon (methyl) acrylate etc. have the acrylic ester monomers such as heterocycle, halogen atom, Siliciumatom;
The ethylene series monomers such as isoprene, divinyl, iso-butylene;
The vinyl ether such as methylvinylether, ethyl vinyl ether is monomer;
Alkene or the dienes such as ethene, divinyl, isoprene, iso-butylene;
The vinyl ethers such as vinyl alkyl ethers;
Vinylchlorid;
And other in polymerization the monomer end of vinyl have macromonomer class of free-radical polymerised vinyl etc.These monomers can be separately with aforementioned (methyl) acrylic ester copolymer or make up and aforementioned (methyl) acrylic ester copolymer.
In the present embodiment, as (methyl) acrylic acid polymer (B), for example can list the multipolymer of cyclohexyl methacrylate (CHMA) and Propenoic acid, 2-methyl, isobutyl ester (IBMA), the multipolymer of cyclohexyl methacrylate (CHMA) and isobornyl methacrylate (IBXMA), the multipolymer of methyl methacrylate (MMA) and isobornyl methacrylate (IBXMA), the multipolymer of cyclohexyl methacrylate (CHMA) and acryloyl morpholine (ACMO), the multipolymer of cyclohexyl methacrylate (CHMA) and diethyl acrylamide (DEAA), the multipolymer of vinylformic acid 1-diamantane ester (ADA) and methyl methacrylate (MMA), the multipolymer of methacrylic acid dicyclo pentyl ester (DCPMA) and isobornyl methacrylate (IBXMA), the multipolymer of methacrylic acid dicyclo pentyl ester (DCPMA) and methyl methacrylate (MMA), the multipolymer of methacrylic acid dicyclo pentyl ester (DCPMA) and NVP (NVP), the multipolymer of methacrylic acid dicyclo pentyl ester (DCPMA) and methacrylic acid hydroxyl ethyl ester (HEMA), the multipolymer of methacrylic acid dicyclo pentyl ester (DCPMA) and vinylformic acid (AA), methacrylic acid dicyclo pentyl ester (DCPMA), cyclohexyl methacrylate (CHMA), isobornyl methacrylate (IBXMA), isobornyl acrylate (IBXA), vinylformic acid dicyclo pentyl ester (DCPA), methacrylic acid 1-diamantane ester (ADMA), vinylformic acid 1-diamantane ester (ADA), each homopolymer of methyl methacrylate (MMA) etc.
And then (methyl) acrylic acid polymer (B) can also import the reactive functional group that has with epoxy group(ing) or isocyanate group.As the example of this functional group, can list hydroxyl, carboxyl, amino, amide group, sulfydryl, also can when making (methyl) acrylic acid polymer (B), use (copolymerization) to have the monomer of this functional group.
In the present embodiment, when (methyl) acrylic acid polymer (B) is made the multipolymer of (methyl) acrylic monomer with ester ring type structure and other (methyl) acrylate monomer or co-polymerized monomer, the containing more than the 5 quality % of whole monomers that ratio can be made as formation (methyl) acrylic acid polymer (B) of (methyl) acrylic monomer with ester ring type structure, be preferably more than the 10 quality %, more preferably more than the 20 quality %, further preferably be made as 30 quality % above (be generally be lower than 100 quality %, be preferably 90 quality % following).(methyl) acrylic monomer with ester ring type structure contains 5 quality % when above, and the little and bonding force can improve low speed and peel off the time of the bounding force when peeling off at a high speed is to not producing the degree of floating, peeling off such problem.When being lower than 5 quality %, cementability, the cementability when especially low speed is peeled off are poor sometimes.
The weight-average molecular weight of (methyl) acrylic acid polymer (B) is more than 1000 and is lower than 30000, is preferably more than 1500 and is lower than 20000, more preferably more than 2000 and be lower than 10000.Weight-average molecular weight is 30000 when above, and the cementability when low speed is peeled off can reduce.In addition, weight-average molecular weight is lower than at 1000 o'clock, thereby can become the reduction of the bounding force (high speed peeling force, low speed peeling force) that lower molecular weight causes adhesive sheet.
The mensuration of the weight-average molecular weight of polymkeric substance (A), (methyl) acrylic acid polymer (B) can be obtained with polystyrene conversion by gel permeation chromatography (GPC) method.Particularly, measure according to the method for putting down in writing among the embodiment described later, condition.
About (methyl) acrylic acid polymer (B), it is desirable to, second-order transition temperature (Tg) is 20 ℃ ~ 300 ℃, is preferably 50 ℃ ~ 280 ℃, more preferably 90 ℃ ~ 280 ℃, more preferably 110 ℃ ~ 250 ℃.When second-order transition temperature (Tg) was lower than 20 ℃, the bonding force when the little and low speed of the bounding force when existence can't realize peeling off is at a high speed peeled off was fully high to not producing this situation of taking into account high speed peeling force and low speed peeling force of the degree of floating, peeling off such problem.
In the present embodiment, the second-order transition temperature that can be used as the representative materials that (methyl) acrylic acid polymer (B) uses is as shown in table 1.Second-order transition temperature shown in the table 1 is the nominal value of the records such as document (polymer handbook, bonding handbook etc.), catalogue, perhaps when (methyl) acrylic acid polymer (B) is multipolymer, be the value of calculating based on aforementioned formula (2) (Fox formula).
Table 1
The composition of (methyl) acrylic acid polymer (B) Tg(℃) Remarks
DCPMA 175 The value of the record such as document
DCPA 120 The value of the record such as document
IBXMA 173 The value of the record such as document
IBXA 97 The value of the record such as document
CHMA 66 The value of the record such as document
CHA 15 The value of the record such as document
IBMA 48 The value of the record such as document
MMA 105 The value of the record such as document
ADMA 250 The value of the record such as document
ADA 153 The value of the record such as document
NVP 54 The value of the record such as document
HEMA 40 The value of the record such as document
DCPMA／MMA=40/60 130 Calculated value (based on the Fox formula)
DCPMA／MMA=60/40 144 Calculated value (based on the Fox formula)
DCPMA／MMA=80／20 159 Calculated value (based on the Fox formula)
DCPMA／NVP=60/40 117 Calculated value (based on the Fox formula)
DC PMA／HEMA=60/40 139 Calculated value (based on the Fox formula)
IBXA／MMA=40/60 130 Calculated value (based on the Fox formula)
CHMA／IBMA=60／40 59 Calculated value (based on the Fox formula)
Abbreviation in the table 1 represents following compound.
DCPMA: methacrylic acid dicyclo pentyl ester
DCPA: vinylformic acid dicyclo pentyl ester
IBXMA: isobornyl methacrylate
IBXA: isobornyl acrylate
CHMA: cyclohexyl methacrylate
CHA: cyclohexyl acrylate
IBMA: Propenoic acid, 2-methyl, isobutyl ester
MMA: methyl methacrylate
ADMA: methacrylic acid 1-diamantane ester
ADA: vinylformic acid 1-diamantane ester
The NVP:N-vinyl-2-pyrrolidone
HEMA: methacrylic acid hydroxyl ethyl ester
(methyl) acrylic acid polymer (B) is made such as utilizing solution polymerization process, mass polymerization, emulsion polymerization, suspension polymerization, mass polymerization etc. to carry out polymerization by (methyl) acrylic monomer that will have said structure.
In order to adjust the molecular weight of (methyl) acrylic acid polymer (B), in its polymerization, can use chain-transfer agent.As the example of employed chain-transfer agent, can list the compound that octyl mercaptan, lauryl mercaptan, uncle's lauryl mercaptan, mercaptoethanol, thioglycerin etc. have sulfydryl; The mercaptoacetate of Thiovanic acid, Methyl Thioglycolate, ethyl thioglycolate, Thiovanic acid propyl ester, Thiovanic acid butyl ester, the Thiovanic acid tert-butyl ester, 2-ethylhexyl mercaptoacetate, Thiovanic acid monooctyl ester, Thiovanic acid ester in the last of the ten Heavenly stems, Thiovanic acid dodecyl ester, ethylene glycol, the mercaptoacetate of neopentyl glycol, the mercaptoacetate classes such as mercaptoacetate of tetramethylolmethane; Alpha-methyl styrene dimer etc.
Consumption as chain-transfer agent, be not particularly limited, usually, with respect to 100 mass parts (methyl) acrylic monomer, contain 0.1 mass parts ~ 20 mass parts, preferably contain 0.2 mass parts ~ 15 mass parts, more preferably contain 0.3 mass parts ~ 10 mass parts chain-transfer agents.By adjusting in this wise the addition of chain-transfer agent, can obtain to have (methyl) acrylic acid polymer (B) of suitable molecular weight.Need to prove, chain-transfer agent can use separately or be used in combination of two or more.
Peel off again and use binder composition
Peeling off again with binder composition of present embodiment contains above-mentioned polymkeric substance (A), (methyl) acrylic acid polymer (B) as essential composition.With respect to 100 mass parts polymkeric substance (A), the content of (methyl) acrylic acid polymer (B) is 0.05 mass parts ~ 3 mass parts, is preferably 0.08 mass parts ~ 2.5 mass parts, more preferably 0.1 mass parts ~ 2 mass parts.When adding (methyl) acrylic acid polymer (B) and surpassing 3 mass parts, can reduce with the transparency of peeling off again with the binder layer of acrylic adhesive composition formation of present embodiment.In addition, when the addition of (methyl) acrylic acid polymer (B) was less than 0.05 mass parts, the bonding force when the little and low speed of the bounding force in the time of can't realizing peeling off is at a high speed peeled off was fully high to not producing taking into account of the such high speed peeling force of the degree of floating, peeling off such problem and low speed peeling force.
Peeling off again with binder composition except above-mentioned polymkeric substance (A), (methyl) acrylic acid polymer (B) of present embodiment can be contained various additives commonly used in the binder composition field as any composition.As described any composition, can tackifying resin, linking agent, catalyzer, softening agent, tenderizer, weighting agent, tinting material (pigment, dyestuff etc.), antioxidant, flow agent, stablizer, sanitas, static inhibitor etc. be shown example.This additive can utilize well-established law to use in the past known additive.
In order to adjust the force of cohesion of peeling off again with binder layer described later, except above-mentioned multi-functional monomer, can also use linking agent.Linking agent can use normally used linking agent, is that linking agent, isocyanate-based linking agent, silicon-type linking agent, oxazoline are that linking agent, aziridine are that linking agent, silane are linking agent, alkyl etherificate melamine series linking agent, metal-chelating system linking agent etc. such as listing epoxy.Especially can use aptly isocyanate-based linking agent, epoxy is linking agent, metal-chelating system linking agent.These compounds can use separately, perhaps also can be used in combination of two or more.
Particularly, as the example of isocyanate-based linking agent, can list the adducts of the polyvalent alcohols such as tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, Xylene Diisocyanate, hydrogenated xylene diisocyanate, diphenylmethanediisocyanate, hydrogenated diphenyl methane diisocyanate, tetramethylxylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, polymethylene multi-phenenyl isocyanate and they and TriMethylolPropane(TMP).Perhaps, can also use the compound that has at least 1 above isocyanate group and 1 above unsaturated link(age) in 1 molecule, particularly, can use (methyl) vinylformic acid 2-isocyanato ethyl ester etc. as the isocyanate-based linking agent.These compounds can use separately, perhaps also can be used in combination of two or more.
Be linking agent as epoxy, can list dihydroxyphenyl propane, Epicholorohydrin type epoxy is resin, diglycidyl ether of ethylene glycol, polyethyleneglycol diglycidylether, glycerin diglycidyl ether, T 55,1,6-hexylene glycol glycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, diglycidylaniline, diamines glycidyl amine, N, N, N ', N '-four glycidyl group-MXDP and 1, two (N, N '-diamines glycidyl-amino methyl) hexanaphthenes of 3-etc.These compounds can use separately, perhaps also can be used in combination of two or more.
As the metal-chelating compounds, can list aluminium, iron, tin, titanium, nickel etc. as metal ingredient, can list acetylene, methyl acetoacetate, ethyl lactate etc. as the inner complex composition.These compounds can use separately, perhaps also can be used in combination of two or more.
Content to the linking agent that uses in the present embodiment is not particularly limited, and usually, with respect to polymkeric substance (A) 100 mass parts, contains 0.01 mass parts ~ 15 mass parts, preferably contains 0.5 mass parts ~ 10 mass parts.When the content of linking agent was lower than 0.01 mass parts, the force of cohesion of tackiness agent diminished, can produce the pollution to adherend sometimes.On the other hand, when content surpasses 15 mass parts, exist the force of cohesion of polymkeric substance large, mobilely reduce, wetting insufficient, situation that cementability reduces.
In the binder composition disclosed herein, can also contain and be useful on the crosslinking catalyst that above-mentioned arbitrary crosslinking reaction is more effectively carried out.As described crosslinking catalyst, for example can preferably use tin series catalysts (particularly dibutyl tin laurate).Consumption to crosslinking catalyst (such as tin series catalysts such as dibutyl tin laurates) is not particularly limited, and for example, with respect to polymkeric substance (A) 100 mass parts, can roughly be made as 0.005 mass parts ~ 1 mass parts.
Binder composition disclosed herein can contain the compound that produces keto-enol tautomerism.For example, but in the binder composition that the binder composition that comprises linking agent or compounding linking agent use, can preferably adopt the embodiment that comprises the compound that produces above-mentioned keto-enol tautomerism.Thus, can suppress excessive viscosity rise, the gelation of the binder composition behind the compounding linking agent, realize prolonging the effect of the working life of said composition.When using at least isocyanate compound as above-mentioned linking agent, it is significant especially containing the compound that produces keto-enol tautomerism.It is organic solvent solution or solvent-free form that this technology for example can preferably be applied to above-mentioned binder composition.
Compound as producing above-mentioned keto-enol tautomerism can use various beta-dicarbonyl compounds.As object lesson, can list methyl ethyl diketone, 2,4-hexanedione, 3,5-heptadione, 2-methyl hexane-3,5-diketone, 6-methylheptane-2,4-diketone, 2,6-dimethyl heptane-3, the beta-diketon classes such as 5-diketone; The acetoacetic esters such as methyl acetoacetate, methyl aceto acetate, ISOPROPYL ACETOACETATE, tert-butyl acetoacetate; The propionyl acetate esters such as Propionylacetic acid ethyl ester, propionyl isopropyl acetate, propionyl tert.-butyl acetate; The isobutyryl acetate esters such as ethyl isobutyryl, ethyl isobutyryl, isobutyryl isopropyl acetate, isobutyryl tert.-butyl acetate; The malonic ester classes such as propanedioic acid methyl esters, malonic ester; Deng.Wherein, the compound as suitable can list methyl ethyl diketone and acetoacetic ester.The compound of described generation keto-enol tautomerism can use separately, also can be used in combination of two or more.
Consumption about the compound that produces keto-enol tautomerism for example can be made as 0.1 mass parts ~ 20 mass parts with respect to polymkeric substance (A) 100 mass parts, preferably is made as 0.5 mass parts ~ 15 mass parts (for example 1 mass parts ~ 10 mass parts).When the consumption of above-claimed cpd is lower than 0.1 mass parts, sometimes be difficult to bring into play sufficient result of use.On the other hand, when the consumption of this compound surpasses 20 mass parts, remain in sometimes and make the force of cohesion reduction in the binder layer.
Peel off again with binder layer and peel off again and use adhesive sheet
Then, to comprise have an above-mentioned composition peel off again peeling off again with binder layer and having to peel off again with peeling off with adhesive sheet again of binder layer and describe with binder composition.
Peeling off can be for peeling off the cured layer with binder composition again with binder layer again.That is, this binder layer can by will peel off again with binder composition give (for example, coating/apply) to suitable supporter, then implement aptly solidification treatment and form.Supporter is when the plastic basis material that antistatic treatment forms, and also can form peel off at antistatic layer again and use binder layer, can also form to peel off at the face without antistatic treatment in addition again and use binder layer.When carrying out two or more solidification treatment (dry, crosslinked, polymerization etc.), these processing can be simultaneously or the multistage carry out.Binder composition for having used partial polymer (acrylic acid polymer slurries) is typically, and as above-mentioned solidification treatment, carries out final copolyreaction (partial polymer is supplied to form complete polymkeric substance in further copolyreaction).For example, if the binder composition of light solidified is then implemented rayed.As required, also can implement the solidification treatment such as crosslinked, dry.For example, in the time of need to making Photocurable adhesive composition dry, after drying, carry out photocuring and get final product.Binder composition for having used complete polymkeric substance is typically, and as above-mentioned solidification treatment, can implement as required drying (heat drying), the processing such as crosslinked.
Peel off again with binder composition coated/apply such as being coated with the habitual coating machine such as machine, knife coater, spraying machine with gravure roll coating machine, reverse roll coater, kiss roll coater, dip roll coating machine, rod and implement.Need to prove, can on supporter, directly give binder composition and form binder layer, also the binder layer that forms at release liner can be transferred on the base material.
In the present embodiment, use binder layer about peeling off again, it is desirable to, the insoluble composition rate of its solvent is 85.00 quality % ~ 99.95 quality %.Be preferably 90.00 quality % ~ 99.92 quality %, more preferably 92.00 ~ 99.90 quality %.When the insoluble composition rate of solvent is lower than 85.00 quality %; sometimes force of cohesion can become insufficient, can produce pollution from adherend (protected body) when peeling off; in addition; when the insoluble composition rate of solvent surpassed 99.95 quality %, force of cohesion too high, the sufficient bounding force (high speed peeling force, low speed peeling force) that becomes was poor sometimes.Need to prove, the evaluation method of the insoluble composition rate of solvent sees below to be stated.
The thickness of peeling off again with binder layer is not particularly limited, usually can be by for example making 3 μ m ~ 60 μ m, preferably make 5 μ m ~ 40 μ m, thus realize good cementability.When the thickness of binder layer was lower than 3 μ m, sometimes cementability deficiency, meeting produced and floats, peels off, on the other hand, when the thickness of binder layer surpasses 60 μ m, sometimes high speed peeling force increase, strip operation reduction.
The peeling off again to possess by peeling off again with peeling off again of forming of binder composition with adhesive sheet of present embodiment used binder layer.Peeling off with adhesive sheet is described binder layer be fixed at least single face of supporter, namely can not arrange from the form of this supporter separation binder layer again.Can comprise the adhesive sheet that is called as self adhesive tape, adhesive film, adhesive label etc. in the concept of adhesive sheet described herein.In addition, according to its use, also can be for be the adhesive sheet of suitable shape through cutting, punch process etc.Need to prove, binder layer is not limited to the binder layer of continuous formation, also can be the binder layer that forms such as the regular or random pattern such as point-like, striated.
As above-mentioned supporter, such as can suitably selecting and use according to the purposes of self adhesive tape the polyolefin films such as polyethylene, polypropylene, poly-1-butylene, poly--4-methyl-1-pentene, ethylene-propylene copolymer, ethene-butene-1 copolymer, vinyl-vinyl acetate copolymer, ethylene ethyl acrylate copolymer, ethylene-vinyl alcohol copolymer; The polyester films such as polyethylene terephthalate, PEN, polybutylene terephthalate; The polyamide layers such as polyacrylate film, polystyrene film, nylon 6, nylon 6,6, partially aromatic polyamide; The plastics films such as polyvinyl chloride film, polyvinylidene chloride film, polycarbonate film;
The foam substrate such as polyurethane foam, polyethylene;
The paper such as kraft paper, goffered paper, Japan paper;
The cloth such as cotton, short fiber cloth;
The non-woven fabrics such as polyester non-woven fabric, vinylon non-woven fabrics;
The tinsel such as aluminium foil, Copper Foil; Deng.With peeling off again with acrylic pressure-sensitive adhesive sheet when the surface protective plate described later of present embodiment, preferably use the plastics films such as polyolefin film, polyester film, polychlorostyrene vinyl film as supporter.In addition, when using surface protective plate in particular as optics, preferably use polyolefin film, pet film, polybutylene terephthalate film, PEN film.As above-mentioned plastics film, can use without any of oriented film and stretching (uniaxial extension or biaxial stretch-formed) film.
In addition, can also to utilize as required silicon-type, fluorine system, chain alkyl system or fatty acid amide be that releasing agent, silicon dioxide powder etc. carry out the easy bonding processing such as the demoulding and antifouling processing, acid treatment, alkaline purification, prime treatment, corona treatment, Cement Composite Treated by Plasma, UV treatment to supporter.The thickness of supporter can suitably be selected according to purpose, generally speaking, probably is 5 μ m ~ 200 μ m(typical case, 10 μ m ~ 100 μ m) about.
It is that releasing agent, silicon dioxide powder etc. carry out the antistatic treatment such as easy bonding processing, application type, mixed milling type, evaporation type such as the demoulding and antifouling processing, acid treatment, alkaline purification, prime treatment, corona treatment, Cement Composite Treated by Plasma, UV treatment that above-mentioned supporter can also utilize silicon-type, fluorine system, chain alkyl system or fatty acid amide as required.
In addition, present embodiment peels off with adhesive sheet employed plastics film more more preferably through the plastics film of antistatic treatment.By carrying out antistatic treatment, can prevent the generation of static, in the optical electron member correlative technology field of the charged problem that becomes especially severe, be useful.The antistatic treatment that plastics film is applied is not particularly limited, and can use normally used at least single face at film that the method for antistatic layer is set or the mixing method that enters the mixed milling type static inhibitor in plastics film.As the method that antistatic layer is set at least single face of film, can list the static resistance resin that is formed by static inhibitor and resinous principle, the method that coating contains the electroconductive resin of electric conductive polymer, conductive material, the method for evaporation or plating conductive material of being coated with.
As the static inhibitor that contains in the static resistance resin, can list quaternary ammonium salt, pyridinium salt, has primary amino, secondary amino group, the cationic static inhibitor of the cationic functional groups such as uncle's amino, has sulfonate, sulfuric acid, phosphonate, the anionic antistatic agent of the anionic property functional groups such as phosphate ester salt, alkyl betaine and derivative thereof, imidazoline and its derivative, the amphoteric such as L-Ala and derivative thereof static inhibitor, amino alcohol and derivative thereof, glycerine and derivative thereof, the non-ionic antistatic agent such as polyoxyethylene glycol and derivative thereof, and then, can enumerate sends as an envoy to have above-mentioned cationic, anionic, the monomer polymerization of the ionic conductivity group of amphoteric ion type or copolymerization and the ionic-conductive polymer that obtains.These compounds can use separately, perhaps can be use mixing two or more.
Particularly, as cationic static inhibitor, such as (methyl) acrylate copolymer that can list alkyl trimethyl ammonium salt, acyl group amido propyl trimethyl ammonium Methylsulfate, alkyl benzyl methyl ammonium salt, acyl group choline chloride 60, poly-dimethylaminoethyl methacrylic ester etc. and have quaternary ammonium group; Polyvinyl benzyl trimethyl ammonium chloride etc. has the styrol copolymer of quaternary ammonium group; Diallyl dimethyl ammoniumchloride etc. have the diallyl amine multipolymer of quaternary ammonium group etc.These compounds can use separately, perhaps also can be use mixing two or more.
As anionic antistatic agent, for example can list alkylsulfonate, alkylbenzene sulfonate, alkyl sulfuric ester salt, AES salt, alkyl phosphate salt, contain the sulfonic benzo ethylene copolymer.These compounds can use separately, perhaps also can be use mixing two or more.
As the amphoteric ion type static inhibitor, for example can list alkyl betaine, alkyl imidazoline trimethyl-glycine, carbonyl trimethyl-glycine graft copolymer.These compounds can use separately, perhaps also can be use mixing two or more.
As non-ionic antistatic agent, such as the multipolymer that can list fatty acid alkyl amide, two (2-hydroxyethyl) alkylamine, polyoxyethylene alkyl amine, glycerin fatty acid ester, cithrol (polyoxyethylene glycol fatty acid ester), sorbitan-fatty acid ester, polyoxy sorbitan-fatty acid ester, polyoxyethylene alkyl phenyl ether, Voranol EP 2001, polyoxyethylene glycol, polyethyleneoxide diamine, formed by polyethers, polyester and polymeric amide, methoxy poly (ethylene glycol) (methyl) acrylate etc.These compounds can use separately, perhaps also can be use mixing two or more.
As electric conductive polymer, such as listing polyaniline, polypyrrole, Polythiophene etc.
As conductive material, for example can list stannic oxide, weisspiessglanz, Indium sesquioxide, Cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold and silver, copper, aluminium, nickel, chromium, titanium, iron, cobalt, cupric iodide and their alloy or mixture.
As the resinous principle that uses in static resistance resin and the electroconductive resin, can use the common resins such as polyester, vinylformic acid, polyethylene, urethane, trimeric cyanamide, epoxy.Need to prove, during for Polymer Antistatic Agent, also can not resinous composition.In addition, can in the antistatic resin composition, contain compound, epoxy compounds, the isocyanic ester based compound such as melamine series, Urea Series, oxalic dialdehyde system, acrylamide of methylolation or alkanol as linking agent.
As the formation method of antistatic layer, for example, dilute above-mentioned static resistance resin, electric conductive polymer, electroconductive resin with organic solvent or water equal solvent, this masking liquid is coated on the plastics film and drying forms.
As the organic solvent that is used to form aforementioned antistatic layer, such as listing methylethylketone, acetone, ethyl acetate, tetrahydrofuran (THF), two oxazoles, pimelinketone, normal hexane, toluene, dimethylbenzene, methyl alcohol, ethanol, n-propyl alcohol, Virahol etc.These solvents can use separately, perhaps also can be use mixing two or more.
About forming the coating process of aforementioned antistatic layer, can suit to use known coating process, particularly, for example can list roller coat, intaglio plate coating, oppositely coating, roller brush, spraying, airblade coating, impregnation and curtain-type coating method.
As the thickness of aforementioned static resistance resin layer, electric conductive polymer, electroconductive resin, be generally 0.01 μ m ~ 5 μ m, be preferably about 0.03 μ m ~ 1 μ m.
As the method for evaporation or the plating of conductive material, such as listing vacuum evaporation, sputter, ion plating, chemical vapor deposition, spraying thermolysis, electroless plating, electrochemical plating etc.
Thickness as aforementioned conductive material layer is generally 2nm ~ 1000nm, is preferably 5nm ~ 500nm.
In addition, as the mixed milling type static inhibitor, can use aptly above-mentioned static inhibitor.As the compounding amount of mixed milling type static inhibitor, take with respect to the gross weight of plastics film below 20 quality %, the scope that is preferably 0.05 quality % ~ 10 quality % uses.As compounding process, so long as aforementioned static inhibitor can be blended in the method for the resin of plastics film equably, then be not particularly limited, such as using warming mill, Banbury mixer, pressurization kneader, twin-screw mixer machine etc.
Peeling off again with adhesive sheet, surface protective plate described later, optics with in the surface protective plate of present embodiment, for the purpose of protection adhesive face, can be as required at the adhesive layer surface release liner of fitting.
Material as consisting of release liner has paper, plastics film, but from the viewpoint of surface smoothness excellence, can use aptly plastics film.As this film; so long as can protect the film of aforementioned adhesion agent layer; then be not particularly limited, such as listing polyethylene film, polypropylene film, polybutene film, polyhutadiene film, poly-methyl pentene film, polyvinyl chloride film, vinyl chloride copolymer film, pet film, polybutylene terephthalate film, polyurethane film, vinyl-vinyl acetate copolymer film etc.
The thickness of aforementioned release liner is generally 5 μ m ~ 200 μ m, is preferably about 10 μ m ~ 100 μ m.In the time of in aforementioned range, because to the applying operability of binder layer and excellent from the strip operation of binder layer, thereby preferred.It is that releasing agent, silicon dioxide powder etc. carry out the antistatic treatment such as the demoulding and antifouling processing, application type, mixed milling type, evaporation type that aforementioned release liner can also utilize silicon-type, fluorine system, chain alkyl system or fatty acid amide as required.
Peeling off again with adhesive sheet of present embodiment has the bonding force fully high characteristic to can not produce the degree of floating, peel off such problem of the little and low speed of bounding force when peeling off at a high speed when peeling off.Peeling off again with the bounding force of adhesive sheet when peeling off at a high speed of present embodiment can be estimated in 180 ° of peel adhesion tests when peeling off under 180 ° of draw speed 30m/ minutes, peel angle, in particular for 2.5N/25mm with next be judged as good.180 ° of peel adhesion are preferably below the 2.2N/25mm, more preferably below the 2.0N/25mm.In addition, the lower value of 180 ° of peel adhesion is not had special requirement, be generally more than the 0.1N/25mm, be preferably more than the 0.2N/25mm.180 ° of peel adhesion tests can be measured according to the method for putting down in writing among the aftermentioned embodiment, condition.
In addition, the bounding force of peeling off again when peeling off with the low speed of adhesive sheet of present embodiment can be estimated with the form of peeling off required time based on the permanent load stripping test, adhesive sheet for wide 10mm, long 50mm, splitting time during take the permanent load of 90 ° of direction load 1.2g can be judged as good as more than 350 seconds the time.The splitting time of permanent load stripping test was preferably more than 400 seconds, more preferably more than 450 seconds.In addition, the higher limit of the splitting time of permanent load stripping test is not had special requirement, be generally below 950 seconds.The detailed conditions of permanent load stripping test is measured according to the method for putting down in writing among the embodiment described later, condition.
And then peeling off again with adhesive sheet of present embodiment has the high such characteristic of the transparency.Peeling off again with the transparency of adhesive sheet of present embodiment can be estimated by mist degree, when particularly mist degree is lower than 10%, then can be judged as good.Mist degree preferably is lower than 5%, more preferably less than 3.5%.The detailed conditions that mist degree is measured is measured according to the method for putting down in writing among the aftermentioned embodiment, condition.
Surface protective plate
As mentioned above; peeling off again of present embodiment used adhesive sheet; the high viewpoint to not producing the such characteristic of the degree of floating, peeling off such problem of bonding force when the little and low speed of the bounding force when peeling off at a high speed from having is peeled off, preferably the surface protective plate as the surface of the various protected bodies of protection uses.The protected body that can use as the surface protective plate of present embodiment; can list and use by comprising the PE(polyethylene), the PP(polypropylene), AB S(acrylonitrile-butadiene-styrene copolymer), SB S(styrene-butadiene-styrene block copolymer), the PC(polycarbonate), PVC(vinylchlorid), the PMMA(plexiglass) the various resins of such acrylic resin; the SUS(stainless steel); the metals such as aluminium, the member of the formation such as glass, automobile (its car body is filmed), material of construction, family's electrical article etc.
With peeling off again with adhesive sheet when the surface protective plate of present embodiment, can directly use above-mentioned peeling off again to use adhesive sheet.Yet particularly when using with sheet as surface protection, from preventing from damaging or the viewpoint of dirt, processibility, supporter preferably uses 10 μ m ~ polyolefin film of 100 μ m, polyester film, polyvinyl chloride film.In addition, the thickness of binder layer preferably is made as about 3 μ m ~ 60 μ m.
The optics surface protective plate
And then the surface protective plate of present embodiment is on the basis of above-mentioned adhesion characteristic, and particularly from the high such characteristic of the transparency, preferably the optics as the surface protection that is used for optical thin film uses with surface protective plate.As the optical thin film that the optics of present embodiment can be used with surface protective plate, can list the Polarizer that uses in the image display devices such as liquid-crystal display, plasma display, OLED display, wave plate, optical compensating film, light diffusing sheet, reflector plate, antireflection sheet, bright enhancement film, transparent conducting film (ito thin film) etc.
The optics of present embodiment can be used for following purposes with surface protective plate: protection purposes of the optical thin film of manufacturers when the manufacturing process of display unit (Liquid Crystal Module) of the image display device such as the protection of the manufacturers of the optical thin films such as above-mentioned Polarizer when optical thin film dispatches from the factory, liquid crystal indicator etc.; and then, the protection purposes of the optical thin film in the various operations of punching press, cutting processing etc.
When using surface protective plate, can directly use above-mentioned peeling off again to use adhesive sheet as optics peeling off again with adhesive sheet of present embodiment.Yet; when particularly using with sheet with surface protection as optics; from preventing from damaging or the viewpoint of pollution, processibility, the transparency, supporter preferably uses polyolefin film, pet film, polybutylene terephthalate film, the PEN film of 10 μ m ~ 100 μ m.In addition, the thickness of tackiness agent preferably is made as about 3 μ m ~ 40 μ m.
The optical thin film of belt surface screening glass
Other embodiment is for being pasted with the optical thin film that optics is used the belt surface screening glass of surface protective plate at above-mentioned optical thin film.The optical thin film of the belt surface screening glass of present embodiment is for being attached to the optical thin film that the single or double of optical thin film forms with above-mentioned optics with surface protective plate.Optical thin film about the belt surface screening glass of present embodiment; the manufacturers of the optical thin films such as above-mentioned Polarizer when optical thin film dispatches from the factory, the manufacturers of the image display device such as liquid crystal indicator when the manufacturing process of display unit (Liquid Crystal Module) and then; in the various operations such as punching press, cutting processing, can prevent that optical thin film from damaging, adhering to dust, dust.In addition, optics is transparent high with surface protective plate, therefore can directly implement to check.And then, unwanted the time, can easily optics be peeled off with surface protective plate and do not make optical thin film, image display device damaged.
As described above, peeling off again of present embodiment is lower than 0 ℃ polymkeric substance (A) 100 mass parts as the second-order transition temperature of adhesive composition by containing with binder composition, weight-average molecular weight is more than 1000 and is lower than (methyl) acrylic acid polymer (B) 0.05 mass parts of 30000 ~ 3 mass parts, described (methyl) acrylic acid polymer comprise have the ester ring type structure (methyl) acrylic monomer as monomeric unit, thereby when using this to peel off again with binder composition formation binder layer, bonding force when the little and low speed of the bounding force when peeling off is at a high speed peeled off is high not to be floated to not producing, peel off the degree of such problem, particularly can improve the transparency.Characteristic from this excellence; to be arranged on peeling off again with adhesive sheet of forming on the supporter with peeling off again of forming of binder composition with binder layer by peeling off again of present embodiment can use with surface protective plate as surface protection sheet, the particularly Chang Zuowei optical thin film for the surface protection of optical thin film.In addition, can also use as be pasted with the optical thin film of optics with the belt surface screening glass of surface protective plate at optical thin film.
Can not reduce the transparency as peeling off again with adhesive sheet, the fully high reason to not producing the degree of floating, peeling off such problem of bonding force when the little and low speed of bounding force when peeling off is at a high speed peeled off, supposition has ester ring type structure (methyl) acrylic monomer as (methyl) acrylic acid polymer of monomeric unit owing to adding to comprise, and the interpolation umber is made as on a small quantity, therefore can not change the physical property of the larger body of bounding force impact when peeling off at a high speed, can improve the larger bonding interface of impact of the bounding force when low speed peeled off.
Embodiment
Below, describing the present invention in detail based on embodiment, the present invention is not subjected to any restriction of these embodiment.
Acrylic acid polymer (A) preparation (2EHA/HEA=96/4)
Drop into 96 mass parts 2-EHAs (2EHA), 4 mass parts vinylformic acid 2-hydroxy methacrylates (HEA) in the four-hole boiling flask that possesses agitating vane, thermometer, nitrogen ingress pipe, condenser, dropping funnel, as 0.2 mass parts 2 of polymerization starter, 2 '-Diisopropyl azodicarboxylate and 150 mass parts ethyl acetate, the limit is slowly stirred the limit and is imported nitrogen, liquid temperature in the flask is remained near 65 ℃, carry out 6 hours polyreactions, prepared acrylic acid polymer (A) solution (40 quality %).The second-order transition temperature that this acrylic acid polymer (A) is calculated by the Fox formula is-68 ℃, and weight-average molecular weight is 550,000.
(methyl) acrylic acid polymer 1(DCPM A=100 as (B) composition) Preparation
Drop into 100 mass parts toluene, 100 mass parts methacrylic acid dicyclo pentyl esters (DCPMA) (trade(brand)name: FA-513M, Hitachi change into industrial and make) in the four-hole boiling flask that possesses agitating vane, thermometer, nitrogen ingress pipe, condenser, dropping funnel and as 3 mass parts Thiovanic acids of chain-transfer agent.Then, in 70 ℃ of lower nitrogen atmospheres, stir after 1 hour, drop into 0.2 mass parts Diisopropyl azodicarboxylate as thermal polymerization, 70 ℃ of lower reactions 2 hours, then 80 ℃ of lower reactions 2 hours.Thereafter, reaction solution is dropped in the atmosphere of 130 ℃ of temperature, drying is removed toluene, chain-transfer agent and unreacted monomer, obtains (methyl) acrylic acid polymer 1 of solid state.The second-order transition temperature of (methyl) acrylic acid polymer 1 of gained is 175 ℃.Weight-average molecular weight is 4600.
(methyl) acrylic acid polymer 2(DCPMA=100 as (B) composition) Preparation
Drop into 100 mass parts toluene, 100 mass parts methacrylic acid dicyclo pentyl esters (DCPMA) (trade(brand)name: FA-513M, Hitachi change into industrial and make) in the four-hole boiling flask that possesses agitating vane, thermometer, nitrogen ingress pipe, condenser, dropping funnel and as 5 mass parts Thiovanic acids of chain-transfer agent.Then, in 75 ℃ of lower nitrogen atmospheres, stir after 1 hour, drop into 0.2 mass parts Diisopropyl azodicarboxylate as thermal polymerization, 75 ℃ of lower reactions 2 hours, then 80 ℃ of lower reactions 2 hours.Thereafter, reaction solution is dropped in the atmosphere of 130 ℃ of temperature, drying is removed toluene, chain-transfer agent and unreacted monomer, obtains (methyl) acrylic acid polymer 2 of solid state.The second-order transition temperature of (methyl) acrylic acid polymer 2 of gained is 175 ℃, and weight-average molecular weight is 3000.
(methyl) acrylic acid polymer 3 as (B) composition (DCPMA/MMA=40/60) preparation
Drop into 100 mass parts toluene, 40 mass parts methacrylic acid dicyclo pentyl esters (DCPMA) (trade(brand)name: FA-513M, Hitachi change into industrial and make), 60 mass parts methyl methacrylates (MMA) in the four-hole boiling flask that possesses agitating vane, thermometer, nitrogen ingress pipe, condenser, dropping funnel and as 3 mass parts Thiovanic acids of chain-transfer agent.Then, in 70 ℃ of lower nitrogen atmospheres, stir after 1 hour, drop into 0.2 mass parts Diisopropyl azodicarboxylate as thermal polymerization, 70 ℃ of lower reactions 3 hours, then 80 ℃ of lower reactions 3 hours.Thereafter, reaction solution is dropped in the atmosphere of 130 ℃ of temperature, drying is removed toluene, chain-transfer agent and unreacted monomer, obtains (methyl) acrylic acid polymer 3 of solid state.The second-order transition temperature of (methyl) acrylic acid polymer 3 of gained is 130 ℃, and weight-average molecular weight is 5100.
(methyl) acrylic acid polymer 4 as (B) composition (DCPMA/NVP=60/40) preparation
Drop into 100 mass parts toluene, 60 mass parts methacrylic acid dicyclo pentyl esters (DCPMA) (trade(brand)name: FA-513M, Hitachi change into industrial and make), 40 mass parts NVPs (NVP) in the four-hole boiling flask that possesses agitating vane, thermometer, nitrogen ingress pipe, condenser, dropping funnel and as 2 mass parts Thiovanic acids of chain-transfer agent.Then, in 70 ℃ of lower nitrogen atmospheres, stir after 1 hour, drop into 0.2 mass parts Diisopropyl azodicarboxylate as thermal polymerization, 70 ℃ of lower reactions 2 hours, then 80 ℃ of lower reactions 2 hours.Thereafter, reaction solution is dropped in the atmosphere of 130 ℃ of temperature, drying is removed toluene, chain-transfer agent and unreacted monomer, obtains (methyl) acrylic acid polymer 4 of solid state.The second-order transition temperature of (methyl) acrylic acid polymer 4 of gained is 117 ℃, and weight-average molecular weight is 24000.
(methyl) acrylic acid polymer 5 as (B) composition (DCPMA/HEMA=80/20) preparation
Drop into 100 mass parts toluene, 80 mass parts methacrylic acid dicyclo pentyl esters (DCPMA) (trade(brand)name: FA-513M, Hitachi change into industrial and make), 20 mass parts methacrylic acid hydroxyl ethyl esters (HEMA) in the four-hole boiling flask that possesses agitating vane, thermometer, nitrogen ingress pipe, condenser, dropping funnel and as 3 mass parts Thiovanic acids of chain-transfer agent.Then, in 70 ℃ of lower nitrogen atmospheres, stir after 1 hour, drop into 0.2 mass parts Diisopropyl azodicarboxylate as thermal polymerization, 70 ℃ of lower reactions 2 hours, then 80 ℃ of lower reactions 2 hours.Thereafter, reaction solution is dropped in the atmosphere of 130 ℃ of temperature, drying is removed toluene, chain-transfer agent and unreacted monomer, obtains (methyl) acrylic acid polymer 5 of solid state.The second-order transition temperature of (methyl) acrylic acid polymer 5 of gained is 139 ℃, and weight-average molecular weight is 5500.
(methyl) acrylic acid polymer 6 as (B) composition (DCPMA/MMA=60/40) preparation
Drop into 100 mass parts toluene, 60 mass parts methacrylic acid dicyclo pentyl esters (DCPMA) (trade(brand)name: FA-513M, Hitachi change into industrial and make), 40 mass parts methyl methacrylates (MMA) in the four-hole boiling flask that possesses agitating vane, thermometer, nitrogen ingress pipe, condenser, dropping funnel and as 3 mass parts Thiovanic acids of chain-transfer agent.Then, in 70 ℃ of lower nitrogen atmospheres, stir after 1 hour, drop into 0.2 mass parts Diisopropyl azodicarboxylate as thermal polymerization, 70 ℃ of lower reactions 3 hours, then 80 ℃ of lower reactions 3 hours.Thereafter, reaction solution is dropped in the atmosphere of 130 ℃ of temperature, drying is removed toluene, chain-transfer agent and unreacted monomer, obtains (methyl) acrylic acid polymer 6 of solid state.The second-order transition temperature of (methyl) acrylic acid polymer 6 of gained is 144 ℃, and weight-average molecular weight is 4600.
(methyl) acrylic acid polymer 7 as (B) composition (DCPMA/MMA=80/20) preparation
Drop into 100 mass parts toluene, 80 mass parts methacrylic acid dicyclo pentyl esters (DCPMA) (trade(brand)name: FA-513M, Hitachi change into industrial and make), 20 mass parts methyl methacrylates (MMA) in the four-hole boiling flask that possesses agitating vane, thermometer, nitrogen ingress pipe, condenser, dropping funnel and as 3 mass parts Thiovanic acids of chain-transfer agent.Then, in 70 ℃ of lower nitrogen atmospheres, stir after 1 hour, drop into 0.2 mass parts Diisopropyl azodicarboxylate as thermal polymerization, 70 ℃ of lower reactions 2 hours, then 80 ℃ of lower reactions 4 hours.Thereafter, reaction solution is dropped in the atmosphere of 130 ℃ of temperature, drying is removed toluene, chain-transfer agent and unreacted monomer, obtains (methyl) acrylic acid polymer 7 of solid state.The second-order transition temperature of (methyl) acrylic acid polymer 7 of gained is 159 ℃, and weight-average molecular weight is 4200.
(methyl) acrylic acid polymer 8 as (B) composition (IBXMA/MMA=40/60) preparation
Drop into 100 mass parts toluene, 40 mass parts isobornyl methacrylates (IBXMA), 60 mass parts methyl methacrylates (MMA) in the four-hole boiling flask that possesses agitating vane, thermometer, nitrogen ingress pipe, condenser, dropping funnel and as 3 mass parts Thiovanic acids of chain-transfer agent.Then, in 70 ℃ of lower nitrogen atmospheres, stir after 1 hour, drop into 0.2 mass parts Diisopropyl azodicarboxylate as thermal polymerization, 70 ℃ of lower reactions 2 hours, then 80 ℃ of lower reactions 2 hours.Thereafter, reaction solution is dropped in the atmosphere of 130 ℃ of temperature, drying is removed toluene, chain-transfer agent and unreacted monomer, obtains (methyl) acrylic acid polymer 8 of solid state.The second-order transition temperature of (methyl) acrylic acid polymer 8 of gained is 130 ℃, and weight-average molecular weight is 4300.
(methyl) acrylic acid polymer 9 as (B) composition (CHMA/IBMA=60/40) preparation
Drop into 60 mass parts cyclohexyl methacrylates (CHMA), 40 mass parts Propenoic acid, 2-methyl, isobutyl esters (IBMA) in the four-hole boiling flask that possesses agitating vane, thermometer, nitrogen ingress pipe, condenser, dropping funnel and as 4 mass parts Thiovanic acids of chain-transfer agent.Then, in 70 ℃ of lower nitrogen atmospheres, stir after 1 hour, be warming up to 90 ℃, mix trade(brand)name " PERHEXYL O " (a day oily company makes) 0.005 mass parts, trade(brand)name " PERHEXYL D " (a day oily company makes) 0.01 mass parts as thermal polymerization.And then, 90 ℃ lower stir 1 hour after, be warming up to 150 ℃ through 1 hour, 150 ℃ of lower stirrings 1 hour.Then, be warming up to 170 ℃ through 1 hour, 170 ℃ of lower stirrings 60 minutes.Then, under 170 ℃ state, reduce pressure, stir and removed residual monomer in 1 hour, obtain (methyl) acrylic acid polymer 9.The second-order transition temperature of (methyl) acrylic acid polymer 9 of gained is 59 ℃, and weight-average molecular weight is 4000.
(methyl) acrylic acid polymer 10 as (B) composition (DCPMA/MMA=60/40) preparation
Drop into 100 mass parts toluene, 60 mass parts methacrylic acid dicyclo pentyl esters (DCPMA) (trade(brand)name: FA-513M, Hitachi change into industrial and make), 40 mass parts methyl methacrylates (MMA) in the four-hole boiling flask that possesses agitating vane, thermometer, nitrogen ingress pipe, condenser, dropping funnel and as 3 mass parts Methyl Thioglycolates of chain-transfer agent.Then, in 70 ℃ of lower nitrogen atmospheres, stir after 1 hour, drop into 0.2 mass parts Diisopropyl azodicarboxylate as thermal polymerization, 70 ℃ of lower reactions 2 hours, follow 80 ℃ of lower reactions after 3 hours, 90 ℃ of lower reactions 1 hour.Thereafter, reaction solution is dropped in the atmosphere of 130 ℃ of temperature, drying is removed toluene, chain-transfer agent and unreacted monomer, obtains (methyl) acrylic acid polymer 10 of solid state.The second-order transition temperature of (methyl) acrylic acid polymer 10 of gained is 144 ℃, and weight-average molecular weight is 4400.
(methyl) acrylic acid polymer 11 as (B) composition (DCPMA/MMA=60/40) preparation
Drop into 100 mass parts ethyl acetate, 60 mass parts methacrylic acid dicyclo pentyl esters (DCPMA) (trade(brand)name: FA-513M, Hitachi change into industrial and make), 40 mass parts methyl methacrylates (MMA) in the four-hole boiling flask that possesses agitating vane, thermometer, nitrogen ingress pipe, condenser, dropping funnel and as 3.5 mass parts α-thioglycerins of chain-transfer agent.Then, in 70 ℃ of lower nitrogen atmospheres, stir after 1 hour, drop into 0.2 mass parts Diisopropyl azodicarboxylate as thermal polymerization, 70 ℃ of lower reactions 2 hours, follow 80 ℃ of lower reactions after 3 hours, 90 ℃ of lower reactions 1 hour.Thereafter, reaction solution is dropped in the atmosphere of 130 ℃ of temperature, drying is removed toluene, chain-transfer agent and unreacted monomer, obtains (methyl) acrylic acid polymer 11 of solid state.The second-order transition temperature of (methyl) acrylic acid polymer 11 of gained is 144 ℃, and weight-average molecular weight is 4300.
(methyl) acrylic acid polymer 12 as (B) composition (DCPMA/MMA=60/40) preparation
Drop into 100 mass parts toluene, 60 mass parts methacrylic acid dicyclo pentyl esters (DCPMA) (trade(brand)name: FA-513M, Hitachi change into industrial and make), 40 mass parts methyl methacrylates (MMA) in the four-hole boiling flask that possesses agitating vane, thermometer, nitrogen ingress pipe, condenser, dropping funnel and as 6 mass parts lauryl mercaptans of chain-transfer agent.Then, in 70 ℃ of lower nitrogen atmospheres, stir after 1 hour, drop into 0.2 mass parts Diisopropyl azodicarboxylate as thermal polymerization, 70 ℃ of lower reactions 3 hours, follow 80 ℃ of lower reactions after 2 hours, 90 ℃ of lower reactions 2 hours.Thereafter, reaction solution is dropped in the atmosphere of 130 ℃ of temperature, drying is removed toluene, chain-transfer agent and unreacted monomer, obtains (methyl) acrylic acid polymer 12 of solid state.The second-order transition temperature of (methyl) acrylic acid polymer 12 of gained is 144 ℃, and weight-average molecular weight is 4200.
(methyl) acrylic acid polymer 13 as (B) composition (DCPMA/MMA=60/40) preparation
Drop into 100 mass parts ethyl acetate, 60 mass parts methacrylic acid dicyclo pentyl esters (DCPMA) (trade(brand)name: FA-513M, Hitachi change into industrial and make), 40 mass parts methyl methacrylates (MMA) in the four-hole boiling flask that possesses agitating vane, thermometer, nitrogen ingress pipe, condenser, dropping funnel and as 0.35 mass parts α-thioglycerin of chain-transfer agent.Then, in 70 ℃ of lower nitrogen atmospheres, stir after 1 hour, drop into 0.2 mass parts Diisopropyl azodicarboxylate as thermal polymerization, 70 ℃ of lower reactions 2 hours, follow 80 ℃ of lower reactions after 5 hours, 90 ℃ of lower reactions 2 hours.Thereafter, reaction solution is dropped in the atmosphere of 130 ℃ of temperature, drying is removed toluene, chain-transfer agent and unreacted monomer, obtains (methyl) acrylic acid polymer 13 of solid state.The second-order transition temperature of (methyl) acrylic acid polymer 13 of gained is 144 ℃, and weight-average molecular weight is 33000.
(methyl) acrylic acid polymer 14(MMA=100 as (B) composition) Preparation
Drop into 100 mass parts toluene, 100 mass parts methyl methacrylates (MMA) in the four-hole boiling flask that possesses agitating vane, thermometer, nitrogen ingress pipe, condenser, dropping funnel and as 3 mass parts Thiovanic acids of chain-transfer agent.Then, in 70 ℃ of lower nitrogen atmospheres, stir after 1 hour, drop into 0.2 mass parts Diisopropyl azodicarboxylate as thermal polymerization, 70 ℃ of lower reactions 2 hours, then 80 ℃ of lower reactions 4 hours.Thereafter, reaction solution is dropped in the atmosphere of 130 ℃ of temperature, drying is removed toluene, chain-transfer agent and unreacted monomer, obtains (methyl) acrylic acid polymer 14 of solid state.The second-order transition temperature of (methyl) acrylic acid polymer 14 of gained is 105 ℃, and weight-average molecular weight is 4400.
Embodiment 1
The preparation of binder composition
In acrylic acid polymer (A) solution (35 quality %) being diluted to solution 500 mass parts (acrylic acid polymer (A) 100 mass parts) that 20 quality % form with ethyl acetate, add 1 mass parts (methyl) acrylic acid polymer 1, the isocyanuric acid ester body of 4 mass parts hexamethylene diisocyanates (trade(brand)name: coronate HX, Japanese polyurethane industrial makes), dibutyl tin laurate (1 quality % ethyl acetate solution) 2 mass parts as crosslinking catalyst, under 25 ℃, carry out approximately 5 minutes mix and blend, preparation binder composition (1).
The making of adhesive sheet
With above-mentioned binder composition (1) be coated on with on the opposite face of the antistatic treatment face of the pet film of antistatic treatment layer (trade(brand)name: DIAFOLE T100G38, resin company of Mitsubishi make, thickness 38 μ m), with 130 ℃ of heating 2 minutes, form the binder layer of thickness 20 μ m.Then, at the organosilicon treated side of the surface of above-mentioned binder layer applying release liner (single face has applied organosilicon pet films that process, thickness 25 μ m), make adhesive sheet.
Embodiment 2
The preparation of binder composition
Except using 1 mass parts above-mentioned (methyl) acrylic acid polymer 2 to replace using 1 mass parts above-mentioned (methyl) acrylic acid polymer 1, similarly to Example 1 operation, preparation binder composition (2).
The making of adhesive sheet
Except using above-mentioned binder composition (2) to replace the above-mentioned binder composition (1), adhesive sheet is made in similarly to Example 1 operation.
Embodiment 3
The preparation of binder composition
Except using 0.1 mass parts (methyl) acrylic acid polymer 3 to replace using 1 mass parts above-mentioned (methyl) acrylic acid polymer 1, similarly to Example 1 operation, preparation binder composition (3).
The making of adhesive sheet
Except using above-mentioned binder composition (3) to replace the above-mentioned binder composition (1), adhesive sheet is made in similarly to Example 1 operation.
Embodiment 4
The preparation of binder composition
Except using 1 mass parts (methyl) acrylic acid polymer 3 to replace using 1 mass parts above-mentioned (methyl) acrylic acid polymer 1, similarly to Example 1 operation, preparation binder composition (4).
The making of adhesive sheet
Except using above-mentioned binder composition (4) to replace the above-mentioned binder composition (1), adhesive sheet is made in similarly to Example 1 operation.
Embodiment 5
The preparation of binder composition
Except using 2 mass parts (methyl) acrylic acid polymer 3 to replace using 1 mass parts above-mentioned (methyl) acrylic acid polymer 1, similarly to Example 1 operation, preparation binder composition (5).
The making of adhesive sheet
Except using above-mentioned binder composition (5) to replace the above-mentioned binder composition (1), adhesive sheet is made in similarly to Example 1 operation.
Embodiment 6
The preparation of binder composition
Except using 1 mass parts (methyl) acrylic acid polymer (4) to replace using 1 mass parts above-mentioned (methyl) acrylic acid polymer 1, similarly to Example 1 operation, preparation binder composition (6).
The making of adhesive sheet
Except using above-mentioned binder composition (6) to replace the above-mentioned binder composition (1), adhesive sheet is made in similarly to Example 1 operation.
Embodiment 7
The preparation of binder composition
Except using 1 mass parts (methyl) acrylic acid polymer (5) to replace using 1 mass parts above-mentioned (methyl) acrylic acid polymer 1, similarly to Example 1 operation, preparation binder composition (7).
The making of adhesive sheet
Except using above-mentioned binder composition (7) to replace the above-mentioned binder composition (1), adhesive sheet is made in similarly to Example 1 operation.
Embodiment 8
The preparation of binder composition
Except using 1 mass parts (methyl) acrylic acid polymer (6) to replace using 1 mass parts above-mentioned (methyl) acrylic acid polymer 1, similarly to Example 1 operation, preparation binder composition (8).
The making of adhesive sheet
Except using above-mentioned binder composition (8) to replace the above-mentioned binder composition (1), adhesive sheet is made in similarly to Example 1 operation.
Embodiment 9
The preparation of binder composition
Use 1 mass parts (methyl) acrylic acid polymer (7) to replace using 1 mass parts above-mentioned (methyl) acrylic acid polymer 1, use isocyanuric acid ester body (manufacturing of Japanese polyurethane industrial, coronate HX) 5.3 mass parts of hexamethylene diisocyanate to replace 4 mass parts, in addition, similarly to Example 1 operation, preparation binder composition (9).
The making of adhesive sheet
Except using above-mentioned binder composition (9) to replace the above-mentioned binder composition (1), adhesive sheet is made in similarly to Example 1 operation.
Embodiment 10
The preparation of binder composition
Except using 1 mass parts (methyl) acrylic acid polymer 8 to replace using 1 mass parts above-mentioned (methyl) acrylic acid polymer 1, similarly to Example 1 operation, preparation binder composition (10).
The making of adhesive sheet
Except using above-mentioned binder composition (10) to replace the above-mentioned binder composition (1), adhesive sheet is made in similarly to Example 1 operation.
Embodiment 11
The preparation of binder composition
Except using 1 mass parts (methyl) acrylic acid polymer 9 to replace using 1 mass parts above-mentioned (methyl) acrylic acid polymer 1, similarly to Example 1 operation, preparation binder composition (11).
The making of adhesive sheet
Except using above-mentioned binder composition (11) to replace the above-mentioned binder composition (1), adhesive sheet is made in similarly to Example 1 operation.
Embodiment 12
The preparation of binder composition
Except using 1 mass parts (methyl) acrylic acid polymer 10 to replace using 1 mass parts above-mentioned (methyl) acrylic acid polymer 1, similarly to Example 1 operation, preparation binder composition (12).
The making of adhesive sheet
Except using above-mentioned binder composition (12) to replace the above-mentioned binder composition (1), adhesive sheet is made in similarly to Example 1 operation.
Embodiment 13
The preparation of binder composition
Except using 1 mass parts (methyl) acrylic acid polymer 11 to replace using 1 mass parts above-mentioned (methyl) acrylic acid polymer 1, similarly to Example 1 operation, preparation binder composition (13).
The making of adhesive sheet
Except using above-mentioned binder composition (13) to replace the above-mentioned binder composition (1), adhesive sheet is made in similarly to Example 1 operation.
Embodiment 14
The preparation of binder composition
Except using 1 mass parts (methyl) acrylic acid polymer 12 to replace using 1 mass parts above-mentioned (methyl) acrylic acid polymer 1, similarly to Example 1 operation, preparation binder composition solution (14).
The making of adhesive sheet
Except using above-mentioned binder composition (14) to replace the above-mentioned binder composition (1), adhesive sheet is made in similarly to Example 1 operation.
Comparative example 1
The preparation of binder composition
Above-mentioned except not using (methyl) acrylic acid polymer 1, similarly to Example 1 operation, preparation binder composition (15).
The making of adhesive sheet
Except using above-mentioned binder composition (15) to replace the above-mentioned binder composition (1), adhesive sheet is made in similarly to Example 1 operation.
Comparative example 2
The preparation of binder composition
Except using 5 mass parts (methyl) acrylic acid polymer 3 to replace using 1 mass parts above-mentioned (methyl) acrylic acid polymer 1, similarly to Example 1 operation, preparation binder composition (16).
The making of adhesive sheet
Except using above-mentioned binder composition (16) to replace the above-mentioned binder composition (1), adhesive sheet is made in similarly to Example 1 operation.
Comparative example 3
The preparation of binder composition
Except using 1 mass parts (methyl) acrylic acid polymer 13 to replace using 1 mass parts above-mentioned (methyl) acrylic acid polymer 1, similarly to Example 1 operation, preparation binder composition (17).
The making of adhesive sheet
Except using above-mentioned binder composition (17) to replace the above-mentioned binder composition (1), adhesive sheet is made in similarly to Example 1 operation.
Comparative example 4
The preparation of binder composition
Use 1 mass parts (methyl) acrylic acid polymer 14 to replace using 1 mass parts above-mentioned (methyl) acrylic acid polymer 1, use isocyanuric acid ester body (trade(brand)name: coronate HX, Japanese polyurethane industrial make) 5.3 mass parts of hexamethylene diisocyanate to replace 4 mass parts, in addition, similarly to Example 1 operation, preparation binder composition (18).
The making of adhesive sheet
Except using above-mentioned binder composition (18) to replace the above-mentioned binder composition (1), adhesive sheet is made in similarly to Example 1 operation.
The composition of embodiment 1 ~ 14, comparative example 1 ~ 4 described binder composition is as shown in table 2.
Table 2
Figure BDA00002167691000521
Abbreviation in the table 2 represents following compound.
2EHA: 2-EHA
HEA: vinylformic acid 2-hydroxy methacrylate
DCPMA: methacrylic acid dicyclo pentyl ester
MMA: methyl methacrylate
The NVP:N-vinyl-2-pyrrolidone
HEMA: methacrylic acid N-hydroxy methacrylate
IBXMA: isobornyl methacrylate
CHMA: cyclohexyl methacrylate
IBMA: Propenoic acid, 2-methyl, isobutyl ester
Test method
The mensuration of molecular weight
The weight-average molecular weight of polymkeric substance and (methyl) acrylic copolymer uses GPC device (device name: HLC-8220GPC, eastern Cao company make) to measure.Condition determination is as follows, converts by polystyrene standard and obtains molecular weight.
Sample concentration: 0.2wt%(tetrahydrofuran (THF) (THF) solution)
Sample injection rate: 10 μ l
Elutriant: THF
Flow velocity: 0.6ml/min
Measure temperature: 40 ℃
Post:
Sample column: TSK guardcolumn Super HZ-H(1 root)+TSK gel Super HZM-H(2 root)
Reference column: TSK gel Super H-RC(1 root)
Detector: differential refractometer (RI)
Need to prove, only (methyl) acrylic copolymer 4(DCPMA/NVP=60/40) measure with following condition.
Sample concentration: 0.1wt%(THF/N, dinethylformamide (DMF) solution)
Sample injection rate: 20 μ l
Elutriant: 10mM-LiBr+10mM-phosphoric acid/DMF
Flow velocity: 0.4ml/min
Measure temperature: 40 ℃
Post:
Sample column: TSK guardcolumn Super AW-H(1 root)+TSK gel Super AWM-H+TSK gel Super AW4000+TSK gel Super AW2500
Reference column: TSK gel Sup er H-RC(1 root)
Detector: differential refractometer (RI)
The mensuration of the insoluble composition rate of solvent
Following the calculating of the insoluble composition rate of solvent: to binder layer sampling 0.1g and precision weighing (quality before the dipping), with its in the ethyl acetate of about 50ml with room temperature (20 ~ 25 ℃) 1 week of dipping, then take out the insoluble composition of solvent (ethyl acetate), descend drying after 2 hours at 130 ℃ the insoluble composition of this solvent, carry out weighing (quality behind the impregnation drying), use the insoluble composition rate of solvent calculating formula " the insoluble composition rate of solvent (quality %)=[(quality behind the impregnation drying)/(quality before the dipping)] * 100 " to calculate.
Low speed stripping test " permanent load is peeled off "
Each embodiment and the described adhesive sheet of comparative example are cut to the size of wide 10mm, long 60mm; after release liner peeled off; (trade(brand)name: SEG 1425DU, eastern electrician of day company make to be crimped on the triacetyl cellulose Polarizer with hand roller; wide: 70mm, length: on surface 100mm); then carry out lamination with 0.25MPa, 0.3m/ minute crimping condition, make assess sample (optical thin film of belt surface screening glass).Behind the above-mentioned lamination, under the environment of 23 ℃ * 50%RH, placed 30 minutes, then, as shown in Figure 1, the reverse side of triacetyl cellulose Polarizer 2 is fixed on the acrylic board 4 with double-faced adhesive tape 3, with permanent load 5(1.2g) be fixed on the one-sided end of adhesive sheet 1.The mode that reaches 90 ° with peel angle begins to peel off carry sample with permanent load.Length 10mm is made as remaining length, measures until the time of the part of remaining lengths 50mm till all peeling off.Be determined under the environment of 23 ℃ * 50%RH and carry out.Be that situation more than 350 seconds is designated as well with the splitting time under the permanent load, the situation that will be lower than 350 seconds is designated as bad.Measurement result is shown in table 3.
High speed stripping test " 180 ° of peel adhesion "
The adhesive sheet of each embodiment and comparative example is cut to the size of wide 25mm, long 100mm; after release liner peeled off; (trade(brand)name: SE G1425DU, eastern electrician of day company make to be crimped on the triacetyl cellulose Polarizer with hand roller; wide: 70mm, length: on surface 100mm); then carry out lamination with 0.25MPa, 0.3m/ minute crimping condition, make assess sample (optical thin film of belt surface screening glass).
Behind the above-mentioned lamination, under the environment of 23 ℃ * 50%RH, placed 30 minutes, then, as shown in Figure 2, the reverse side of triacetyl cellulose Polarizer 2 is fixed on the acrylic board 4 with double-faced adhesive tape 3, measures with universal tensile testing machine with draw speed 30m/ minute, bounding force when peel off 180 ° of one-sided ends to adhesive sheet 1 of peel angle.Be determined under the environment of 23 ℃ * 50%RH and carry out.The situation that bounding force when high speed is peeled off is lower than 2.5N/25mm is designated as well, is designated as the situation more than the 2.5N/25mm bad.Measurement result is shown in table 3.
Transparency test: mist degree
Each embodiment and the described adhesive sheet of comparative example are cut to the size of wide 50mm, long 50mm, then, release liner are peeled off, with haze meter (manufacturings of dye technology institute of Murakami K. K.) mensuration mist degree.Mist degree is lower than 10% situation and is designated as well, be designated as the situation more than 10% bad.Measurement result is shown in table 3.
Table 3
As shown in table 3, can confirm, for not use weight-average molecular weight be more than 1000 and be lower than 30000, comprise (methyl) acrylic monomer with ester ring type structure as the comparative example 1 of (methyl) acrylic acid polymer (B) of monomeric unit, bounding force when its low speed is peeled off is insufficient, in addition, add the transparency of comparative example 2 of above (methyl) acrylic acid polymer (B) of 3 mass parts obviously poor.In addition, can confirm, having used weight-average molecular weight is that the low speed of the comparative example 3 of (methyl) acrylic acid polymer (B) more than 30000 bounding force when peeling off is insufficient.And then, can confirm, used the bounding force when not containing (methyl) acrylic monomer with ester ring type structure and peeling off as the low speed of the comparative example 4 of (methyl) acrylic acid polymer (B) of monomeric unit insufficient.
In addition, in all embodiments, can be observed taking into account of high speed separability and low speed separability.In addition, the transparency is also good.
The present invention described above is summarized as following project.
Project 1
A kind of peeling off again used binder composition, it is characterized in that, it comprises:
Second-order transition temperature is lower than 0 ℃ polymkeric substance (A) 100 mass parts; And
Weight-average molecular weight is more than 1000 and is lower than (methyl) acrylic acid polymer (B) 0.05 mass parts of 30000 ~ 3 mass parts, described (methyl) acrylic acid polymer (B) comprises represented (methyl) acrylic monomer with ester ring type structure of following general formula (1) as monomeric unit
CH 2=C（R 1）COOR 2（1）
[in the formula (1), R 1Be hydrogen atom or methyl, R 2For having the ester ring type alkyl of ester ring type structure].
Project 2
Use binder composition according to project 1 described peeling off again, wherein, aforementioned polymer (A) is acrylic acid polymer.
Project 3
Use binder composition according to project 1 or 2 described peeling off again, wherein, aforementioned ester ring type alkyl with ester ring type structure has caged scaffold.
Project 4
Use binder composition according to each described peeling off again in the project 1 ~ 3, wherein, the second-order transition temperature of aforementioned (methyl) acrylic acid polymer (B) is 20 ℃ ~ 300 ℃.
Project 5
A kind of peeling off again used binder layer, and it is formed by each described peeling off with binder composition again in the project 1 ~ 4.
Project 6
Use binder layer according to project 5 described peeling off again, it comprises the insoluble composition of solvent of 85.00 ~ 99.95 quality %.
Project 7
A kind of peeling off again used adhesive sheet, and it is that project 5 or the 6 described at least single faces that are formed at supporter with binder layer of peeling off are again formed.
Project 8
Use adhesive sheet according to project 7 described peeling off again, wherein, aforementioned supporter is the plastics film that forms through antistatic treatment.
Project 9
A kind of surface protective plate, it is formed by project 7 or 8 described peeling off with adhesive sheet again.
Project 10
A kind of optics surface protective plate, it is formed by project 9 described surface protective plates, is used for the surface protection of optical thin film.
Project 11
A kind of optical thin film of belt surface screening glass, it is pasted with project 10 described optics surface protective plates at optical thin film.

Claims (11)

1. peel off and use binder composition for one kind, it is characterized in that, it comprises:
Second-order transition temperature is lower than 0 ℃ polymkeric substance (A) 100 mass parts; And
Weight-average molecular weight is more than 1000 and is lower than (methyl) acrylic acid polymer (B) 0.05 mass parts of 30000 ~ 3 mass parts, described (methyl) acrylic acid polymer (B) comprises represented (methyl) acrylic monomer with ester ring type structure of following general formula (1) as monomeric unit
CH 2=C（R 1）COOR 2（1）
In the formula (1), R 1Be hydrogen atom or methyl, R 2For having the ester ring type alkyl of ester ring type structure.
2. according to claim 1 peeling off again used binder composition, and wherein, described polymkeric substance (A) is acrylic acid polymer.
3. according to claim 1 and 2 peeling off again used binder composition, and wherein, described ester ring type alkyl with ester ring type structure has caged scaffold.
4. according to claim 1 and 2 peeling off again used binder composition, and wherein, the second-order transition temperature of described (methyl) acrylic acid polymer (B) is 20 ℃ ~ 300 ℃.
5. peel off and use binder layer for one kind, it is formed by claim 1 or 2 described peeling off with binder composition again.
6. according to claim 5 peeling off again used binder layer, and it comprises the insoluble composition of solvent of 85.00 ~ 99.95 quality %.
7. peel off and use adhesive sheet for one kind, it is that at least single face that is formed on supporter with binder layer of peeling off again claimed in claim 5 is formed.
8. according to claim 7 peeling off again used adhesive sheet, and wherein, described supporter is the plastics film that forms through antistatic treatment.
9. surface protective plate, it is formed by claimed in claim 7 peeling off with adhesive sheet again.
10. optics surface protective plate, it is formed by surface protective plate claimed in claim 9, is used for the surface protection of optical thin film.
11. the optical thin film of a belt surface screening glass, it is pasted with optics surface protective plate claimed in claim 10 at optical thin film.
CN2012103533193A 2011-09-20 2012-09-20 Peelable pressure-sensitive adhesive composition, peelable pressure-sensitive adhesive layer, and peelable pressure-sensitive adhesive sheet Pending CN103013398A (en)

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